Co-reporter:Fei LiLianghui Wang, Junjie Wang, Dan Peng, Yuqi Zhao, Shengli Li, Hongping Zhou, Jieying Wu, Xiaohe Tian, Yupeng Tian
Organic Letters 2017 Volume 19(Issue 5) pp:
Publication Date(Web):February 13, 2017
DOI:10.1021/acs.orglett.7b00067
The KOtBu-mediated three-component coupling reaction of indoles, [60]fullerene, and haloalkane has been developed as a practical and efficient protocol for the one-pot synthesis of various 1,4-(3-indole)(organo)[60]fullerenes. The reaction exhibits high regioselectivity at the 3-position of indoles and the 1,4-position on the [60]fullerene core. Furthermore, this methodology features excellent functional group tolerance, such as chloro, ester, cyano, and nitro on indole.
Co-reporter:Dajun Wu, Lufei Xiao, Yanan Shi, Qiong Zhang, Wei Du, Jun Zhang, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian
Journal of Organometallic Chemistry 2017 Volume 830(Volume 830) pp:
Publication Date(Web):15 February 2017
DOI:10.1016/j.jorganchem.2016.12.012
•A series of metal complexes based on the ferrocenyl terpyridine were synthesized and fully characterized.•The electrochemical properties of the complexes 1-6 were studied by cyclic voltammetric experiments.•The third-order nonlinear optical properties in the near-IR range were investigated by the Z-scan technique.A series of zinc (II) and cadmium (II) complexes based on the ferrocenyl terpyridine were synthesized and fully characterized. Firstly, their structures were confirmed by single crystal X-ray diffraction analysis, which revealed that the central metal atom adopted a distorted tetragonal pyramidal geometry coordination model. Secondly, the photophysical properties of the complexes were investigated with aid of experimental and theoretical calculation methods. The results indicate that there are ICT, π⋯π*, LLCT and LMCT transition in the six complexes. Thirdly, their electrochemical behaviors showed that the ferrocenyl (Fc) terpyridine complexes exhibited a quasi-reversible Fc+-Fc redox couple. The E1/2 values of them were influenced by different halides. Lastly, the third-order nonlinear optical properties in the near-IR range were systematically determined by open/close aperture Z-scan methods using tunable femtosecond laser. The results revealed that LCdBr2 possesses largest 2 PA coefficient (β = 0.416 cm/GW) and cross sections (σ = 17835 GM) compared to others. However, the LZnBr2 possess largest values of the cubic hyperpolarizability χ(3) (5.64 × 10−13 esu), it shows that the ferrocenyl-based metal bromine complexes have better NLO properties.A series of novel D-A Cd(II) and Zn(II) Complexes have been synthesized and fully characterized. They have potential applications as NLO materials in near-infrared region.Download high-res image (202KB)Download full-size image
Co-reporter:Xiaohe Tian, Yingzhong Zhu, Mingzhu Zhang, Jingyun Tan, Qiong Zhang, Xingyu Wang, Jiaxiang Yang, Hongping Zhou, Jieying Wu, Yupeng Tian
Dyes and Pigments 2017 Volume 139(Volume 139) pp:
Publication Date(Web):1 April 2017
DOI:10.1016/j.dyepig.2016.12.052
•Large two-photon action cross-section with small molecular weight.•Effective live cell mitochondria staining.•Mild Acidic-enhanced Mitochondrial-targeting.•Long term monitoring with low molar concentration.Compared to cationic molecules, neutral mitochondrial targeting probes rarely exist. Herein, neutral thiophene based terpyridine (-β, -γ) organic probes have been synthesized and systematically characterized. The results from photophysical property investigations indicate that all the compounds possess considerable two-photon activities, and one of these probes possesses the largest two-photon action cross section (Φδmax) value (OT1, 850 nm, ∼370 GM) compared with previously reported mitochondrial imaging agents. Importantly, such probe in mild acidic external environment can trigger significant protonation, and subsequently enhance mitochondrial-labeling using around 10−8 M range concentrations for days. This result may offer a novel strategy to design the probes for mitochondria.
Co-reporter:Xiaohe Tian, Sajid Hussain, Hui Wang, Qiong Zhang, Meng Zhao, Junyang Chen, Hui Zhang, Hongping Zhou, Yan Chen, Yupeng Tian
Dyes and Pigments 2017 Volume 147(Volume 147) pp:
Publication Date(Web):1 December 2017
DOI:10.1016/j.dyepig.2017.07.025
Convenient and rational design of small molecular weight, water-soluble, two-photon excited fluorescence (TPEF) probes remains a challenge for practical biological applications. In this study, we designed six novel water-soluble, near infrared TPEF probes (NL1-3, PL1-3), bearing N-methyl pyridinium moiety, which are specifically sensitive to local viscosity. Fluorescence emission bands and two-photon absorption cross-sections of the title compounds showed a significant enhancement with increased solvent viscosity. The compound NL1, a high fluorescent probe that selectively targeted the mitochondria and was sensitive to mitochondrial environment changes, could be applied to differentiate between nystatin treated and normal cell mitochondrial environment. Furthermore, NL1 is membrane potential independent, which was rarely found in contemporary probes. In addition to two-photon confocal microscopy, NL1 also displayed successful mitochondrial staining under stimulated emission depletion (STED) nanoscopy in living cells. In a nutshell, the merits of near infra-red region (NIR) operation, high selectivity, and signal ratio of these probes facilitate the study of mitochondrial targeting, localization processes, and mitochondria microenvironment related diseases.
Co-reporter:Qiong Zhang;Rongting Guan;Xiaohe Tian;Lei Luo;Hongping Zhou;Shengli Li;Jieying Wu;Yupeng Tian
RSC Advances (2011-Present) 2017 vol. 7(Issue 32) pp:20068-20075
Publication Date(Web):2017/03/31
DOI:10.1039/C7RA00380C
Small, biocompatible and water-soluble molecules with moderate two-photon absorption (2PA) cross-section values (σ) are in extreme demand for specific bioimaging applications. Herein, two novel imidazole–pyrimidine hexafluorophosphate derivatives (6P and 10P) are efficiently synthesized through improved Knoevenagel condensation and Ullmann reactions with high yield. Based on systematic photophysical investigations and theoretical calculations, the structure–property relationships indicate that the different donor groups have large influences on their optical properties. The 2PA cross-section values (σ) are obtained both by Z-scan and two-photon excited fluorescence (2PEF) measurements. It is found that the two-photon absorption cross section values (σ) in the near-infrared region are significantly enhanced for 6P and 10P, which confirms that these small molecules display a suitable turn-ON fluorescence response for two-photon fluorescence microscopy (2PFM). Comprehensively considering the high solubility of the introduced hexafluorophosphate group, 6P and 10P possess high specificity for mitochondrial localization, showing a temperature-independent pathway, possibly passive infusion, which is advantageous in comparison with the commercially available mitochondrial trackers. Due to their low cytotoxicity, these small molecules offer a promising platform to directly monitor the intestinal system in live zebrafish larvae.
Co-reporter:Jun Zhang;Meng Zhao;Wenjie Xie;Jie Jin;Fazhi Xie;Xiaojie Song;Shengyi Zhang;Jieying Wu;Yupeng Tian
New Journal of Chemistry (1998-Present) 2017 vol. 41(Issue 17) pp:9152-9158
Publication Date(Web):2017/08/21
DOI:10.1039/C7NJ00524E
A series of Cd(II) compounds, abbreviated as {[Cd·L·(BTC)0.5·H2O]·(H2O)3}n (1), [Cd5·(PO4)2·(HPO4)2·(H2O)4]n (2) and {[Cd2.5·L·(BTC)1.5·(H2O)1.5·(DMF)]·(H2O)2.35}n (3), were obtained by using a zwitterionic ligand (1,1′,1′′-(2,4,6-trimethybenzene-1,3,5-triyl)-tris(methylene)tris(4-carboxypyridinium) tribromide, H3LBr3) and an aromatic secondary ligand (H4BTC). Structure determination confirmed that compounds 1 and 3 possess the structure of 1D and 2D metal–organic frameworks respectively while compound 2 belongs to a novel inorganic crystal, which may be produced by introducing different categories and concentrations of inorganic acids. In addition to reasonable thermal stability (up to 300 °C), the titled Cd(II) compounds exhibited different photoluminescence emissions in the solid state resulting from coordination environments and crystal structures. Moreover, compound 3 also exhibited a ferroelectric behavior with a saturated spontaneous polarization (Ps) of 0.20 μC cm−2, indicating that compound 3 is a potential ferroelectric material at room temperature.
Co-reporter:Lin Kong;Xiao-he Tian;Hui Wang;Yuan-hao Gao;Qiong Zhang;Jia-xiang Yang;Hong-ping Zhou;Sheng-yi Zhang
Nanoscale (2009-Present) 2017 vol. 9(Issue 23) pp:7901-7910
Publication Date(Web):2017/06/14
DOI:10.1039/C6NR08883J
Coordination coupling induced self-assembly of ZnS microparticles was performed with the help of a π-conjugated sulphur-terminal Zn(II) complex ZnS2L (L = N-hexyl-3-{2-[4-2,2′:6′,2′′-terpyridin-4′-yl-phenyl]ethenyl}-carbazole). The interactions between ZnS and ZnS2L components at the interface, which were analyzed by far-IR and XPS, resulted in a tunable single-photon excited fluorescence and an enhanced nonlinear optical response, including a two-photon absorption cross section and a two-photon excited fluorescence. Such an enhancement in nonlinear optical properties was triggered by the coordination coupling effect between terminal S atoms of ZnS2L and naked Zn2+ ions at the surface of ZnS particles. Thus, the novel hybrid system displayed a unique two-photon excited fluorescence to facilitate promising two-photon microscopy imaging of HepG2 cells upon NIR light illumination at 840 nm. The hybrid shows a stronger ability to enter the cells than free ZnS2L.
Co-reporter:Yiwen Tang;Ming Kong;Xiaohe Tian;Jinghang Wang;Qingyuan Xie;Aidong Wang;Qiong Zhang;Hongping Zhou;Jieying Wu;Yupeng Tian
Journal of Materials Chemistry B 2017 vol. 5(Issue 31) pp:6348-6355
Publication Date(Web):2017/08/09
DOI:10.1039/C7TB01063J
Two-photon (TP) microscopy has advantages for biological imaging in that it allows deeper tissue-penetration and excellent resolution compared with one-photon (OP) microscopy. Herein, two-photon activated nonlinear optical (NLO) materials, a terpyridine derivative ligand with a donor–acceptor (D–A) model and its corresponding four zinc(II) complexes (Z1–Z4), were assembled and fully characterized. Based on their systematic photophysical investigations, it was found that the third-order NLO response in the near-infrared (NIR) region was significantly enhanced for the symmetrical complex Z4 compared with the other asymmetric complexes (Z1–Z3). To further explore its utility in biological systems, Z4 was selected as a two-photon probe for cellular lipid membranes, which was confirmed both by two-photon confocal microscopy and transmission electron microscopy (TEM). Furthermore, it was found that the fluorescence intensity was enhanced for complex Z4 with the addition of bioactive liposomes (1 μg mL−1). Its recognition mechanism was demonstrated by experimental methods, as well as molecular modeling calculations. These findings should open a new pathway for functional metal complexes as lipid membrane targeting probes.
Co-reporter:Yiwen Tang;Ming Kong;Xiaohe Tian;Jinghang Wang;Qingyuan Xie;Aidong Wang;Qiong Zhang;Hongping Zhou;Jieying Wu;Yupeng Tian
Journal of Materials Chemistry B 2017 vol. 5(Issue 31) pp:6348-6355
Publication Date(Web):2017/08/09
DOI:10.1039/C7TB01063J
Two-photon (TP) microscopy has advantages for biological imaging in that it allows deeper tissue-penetration and excellent resolution compared with one-photon (OP) microscopy. Herein, two-photon activated nonlinear optical (NLO) materials, a terpyridine derivative ligand with a donor–acceptor (D–A) model and its corresponding four zinc(II) complexes (Z1–Z4), were assembled and fully characterized. Based on their systematic photophysical investigations, it was found that the third-order NLO response in the near-infrared (NIR) region was significantly enhanced for the symmetrical complex Z4 compared with the other asymmetric complexes (Z1–Z3). To further explore its utility in biological systems, Z4 was selected as a two-photon probe for cellular lipid membranes, which was confirmed both by two-photon confocal microscopy and transmission electron microscopy (TEM). Furthermore, it was found that the fluorescence intensity was enhanced for complex Z4 with the addition of bioactive liposomes (1 μg mL−1). Its recognition mechanism was demonstrated by experimental methods, as well as molecular modeling calculations. These findings should open a new pathway for functional metal complexes as lipid membrane targeting probes.
Co-reporter:Yingzhong Zhu;Wei Du;Mingzhu Zhang;Ying Xu;Leilei Song;Qiong Zhang;Xiaohe Tian;Hongping Zhou;Jieying Wu;Yupeng Tian
Journal of Materials Chemistry B 2017 vol. 5(Issue 21) pp:3862-3869
Publication Date(Web):2017/05/31
DOI:10.1039/C7TB00726D
It is believed that HSO3− and SO32− play important roles in several physiological processes. However, probes with two-photon absorption to detect HSO3− or SO32− in living cells are still limited. Herein, a series of novel indolium derivatives (L1–L4) with an A–π–A′ structure was designed and synthesized as ratiometric probes to detect HSO3−/SO32−in vitro. L3 and L4 display a colorimetric and ratiometric fluorescence dual response to HSO3−/SO32− with a very fast (∼15 s) and high specificity, as well as low detection limits (∼22 nM). Furthermore, their detection is also carried out by using a two-photon excited fluorescence method. A nucleophilic addition reaction is proposed for the sensing mechanism, which is supported by MS, 1H NMR, and density functional theory (DFT) investigations. Importantly, L3 was successfully used for detecting intrinsically generated intracellular HSO3−/SO32− in cancerous cells under one- and two-photon excited fluorescence imaging.
Co-reporter:Jian Su;Jun Zhang;Xiaohe Tian;Meng Zhao;Tao Song;Jiancan Yu;Yuanjing Cui;Guodong Qian;Hong Zhong;Lei Luo;Yujin Zhang;Chuankui Wang;Shengli Li;Jiaxiang Yang;Hongping Zhou;Jieying Wu;Yupeng Tian
Journal of Materials Chemistry B 2017 vol. 5(Issue 27) pp:5458-5463
Publication Date(Web):2017/07/12
DOI:10.1039/C6TB03321K
How can imaging be improved? Coordination polymers (CPs) show fascinating potential in optoelectronic optics but limited potential in bioimaging. Without doubt, it was very meaningful when CPs were first used in second-harmonic generation (SHG) imaging. Herein, through reasonable design and synthesis, a series of nonlinear optical CPs bearing very good one-photon excited fluorescence (OPEF), two-photon excited fluorescence (TPEF) and very strong SHG properties has been presented. Further study demonstrated that the nanoscale CPs show very strong SHG signals which have been applied in the three-dimensional imaging of thick block tissue with higher spatial resolution through simultaneous multichannel nonlinear optical (NLO) imaging technology. After simple encapsulation by polymeric micelles, the nanoscale CPs were successfully applied in SHG bio-imaging within the living cells. This finding throws light on the design of nanoscale NLO CPs and offers a simple avenue to develop novel effective exogenous SHG imaging agents.
Co-reporter:Xiaohe Tian;Qiong Zhang;Mingzhu Zhang;Kajsa Uvdal;Qin Wang;Junyang Chen;Wei Du;Bei Huang;Jieying Wu;Yupeng Tian
Chemical Science (2010-Present) 2017 vol. 8(Issue 1) pp:142-149
Publication Date(Web):2016/12/19
DOI:10.1039/C6SC02342H
Small, biocompatible and water-soluble molecules with high two-photon absorption (2PA) cross-section values (δ) are in high demand for specific bioimaging applications. Here, two novel terpyridine derivative ligands with donor–acceptor (D–A) (L1) and donor–π–acceptor (D–π–A) (L2) models, and their corresponding Zn(II) complexes are designed and characterized. It was found that the two-photon absorption cross section values (δ) in the near-infrared region (NIR, about 800 nm) are significantly enhanced for complexes 1 and 2 compared to their free D–A type ligand L1, while those of complexes 3 and 4 were greatly decreased relative to their free ligand L2, thus confirming that the smaller ligand (D–A type) displays a suitable Turn-ON fluorescence pair for two-photon fluorescence microscopy (2PFM). Firstly, the potential of simultaneously labeling a live cell plasma membrane and nucleus using complex 1 is demonstrated. In addition, live larval and adult zebrafish incubated with an optimal concentration of 1 demonstrated clear brain uptake. Lastly and importantly, using such a probe to visualize the blood–brain-barrier (BBB) capillary endothelial cells and penetrate the BBB into the central nervous system (CNS) intravenously in a mouse model is also explored.
Co-reporter:Xiaohe Tian;Yingzhong Zhu;Mingzhu Zhang;Lei Luo;Jieying Wu;Hongping Zhou;Lijuan Guan;Giuseppe Battaglia;Yupeng Tian
Chemical Communications 2017 vol. 53(Issue 23) pp:3303-3306
Publication Date(Web):2017/03/16
DOI:10.1039/C6CC09470H
We present a two-photon (2P, 800 nm) PDT cyclometalated Iridium(III) complex (Ir-Es) that targets the intracellular nucleus. The complex is capable of migrating sequentially from the nucleus to mitochondria and inducing dual-damage under light exposure. This study suggests that with minor modification of the terminal moieties of complexes, their final intracellular destinations and PDT efficiency can be significantly impacted.
Co-reporter:Hui Liu, Liangtao Wu, Fei Li, Xingyu Wang, Hui Pan, Yanhan Ni, Jiaxiang Yang, Shengli Li, Yupeng Tian, Jieying Wu
Polyhedron 2017 Volume 121() pp:53-60
Publication Date(Web):10 January 2017
DOI:10.1016/j.poly.2016.09.025
A novel dithiocarbazate derivative ligand based on triphenylamine with D-π-A model (HL) and its corresponding transition metal complexes were designed, synthesized and fully characterized. The crystal structures of NiL2 and CuL2 have been confirmed by single crystal X-ray diffraction analysis, indicating that the coordinates to metal-ion to form a five-membered chelated ring with an excellent square-planar conformation, which further form high electron delocalization. Crystal structure determination also confirmed that the structures of NiL2 and CuL2 are isostructural. Open and closed aperture Z-scan measurements were devoted to explore the third-order nonlinear optical (NLO) properties with the aid of femtosecond pulse laser from 680 to 1080 nm. The results revealed that complexes NiL2 and CuL2 possessed large 2PA cross-sections 11235.33 and 12018.99 GM, as well as optical power limiting properties.Two novel D-π-A Ni(II) and Cu(II) complexes have been designed, synthesized and fully characterized. They have potential applications as NLO materials in near-infrared region.
Co-reporter:Xiaohe Tian;Yingzhong Zhu;Qiong Zhang;Ruilong Zhang;Jieying Wu;Yupeng Tian
Chemical Communications 2017 vol. 53(Issue 56) pp:7941-7944
Publication Date(Web):2017/07/11
DOI:10.1039/C7CC03640J
We reported a simple and universal strategy by tuning halides (Cl, Br and I) in terpyridine–Zn(II) complexes to achieve different subcellular organelle targeting (nucleolus, nucleus and intracellular membrane systems, respectively) via different cellular uptake mechanisms, resulting from halide triggering different polymorphs of these complexes.
Co-reporter:Xiaohe Tian;Yingzhong Zhu;Qiong Zhang;Ruilong Zhang;Jieying Wu;Yupeng Tian
Chemical Communications 2017 vol. 53(Issue 56) pp:7941-7944
Publication Date(Web):2017/07/11
DOI:10.1039/C7CC03640J
We reported a simple and universal strategy by tuning halides (Cl, Br and I) in terpyridine–Zn(II) complexes to achieve different subcellular organelle targeting (nucleolus, nucleus and intracellular membrane systems, respectively) via different cellular uptake mechanisms, resulting from halide triggering different polymorphs of these complexes.
Co-reporter:Shichao Wang, Shasha Xu, Yiming Wang, Xiaohe Tian, Yujin Zhang, Chuankui Wang, Jieying Wu, Jiaxiang Yang, Yupeng Tian
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2017 Volume 173() pp:871-879
Publication Date(Web):15 February 2017
DOI:10.1016/j.saa.2016.10.059
•Two novel D-π-D type triphenylamine chromophores with long π-conjugated bridge and strong electron-donating moiety were reported.•The centrosymmetric structures were determined by single crystal X-ray diffraction analysis.•Two chromophores both exhibited intense and wide-dispersed one-photon/two-photon excited fluorescence, bear prodigious 2PA cross section (δ).•Dye2 could effectively uptake toward living cells and display a uniformly localized in cytosolic space.Two centrosymmetric D-π-D type triphenylamine chromophores with long π-conjugated bridge and strong electron-donating moiety were designed, synthesized and fully characterized. The crystal analysis revealed that multiple CH ⋯ π interactions existed in two chromophores, which played a crucial role in generating molecular 1D chains and 2D layers structures. Linear and nonlinear optical properties of the chromophores were systematically investigated with the aid of theoretical calculations. Two chromophores both exhibited intense and wide-dispersed one-photon/two-photon excited fluorescence, bear prodigious 2PA cross section (δ). Especially for Dye2, with ethyoxyl groups, displayed the strong 2PA activity, large cross-sections (δmax > 16,000 GM) and high NLO efficiency (δmax/MW > 16 GM/(g·mol)) in the range of 680–830 nm in DMF. In addition, one- and two-photon fluorescence microscopy images of HepG2 cells incubated with Dye2 were obtained and found that Dye2 could effectively uptake toward living cells and display a uniformly localized in cytosolic space.
Co-reporter:Yiwen Tang, Hui Liu, Hui Zhang, Dandan Li, Jian Su, Shengyi Zhang, Hongping Zhou, Shengli Li, Jieying Wu, Yupeng Tian
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2017 Volume 175() pp:92-99
Publication Date(Web):15 March 2017
DOI:10.1016/j.saa.2016.12.017
•Three stilbazolium salts with A-π-A model have been synthesized and fully characterized.•A relative strong intramolecular charge transfer (ICT) transition•The excellent third-order NLO response in the near-infrared (IR) region by Z-scan technique using femtosecond laser.•The different terminal substituent group of the pyridinium plays a vital role in third-order NLO behavior.A series of water-soluble stilbazolium salts with A-π-A (A: Acceptor) model have been synthesized and fully characterized. The results obtained from absorption spectra and TD-DFT computational studies show that there is a relative strong intramolecular charge transfer (ICT) transition from pyridine unit to pyridine cation of the stilbazolium salts. Furthermore, it is found that the three stilbazolium salts (T1, T2, T3) show the strong two-photon absorption (2PA) response in the near-infrared (IR) region by Z-scan technique using femtosecond laser. And the stilbazolium salt T3 shows the largest two-photon absorption cross-section and third-order nonlinear optical (NLO) coefficient χ(3) at 730 nm, indicating the different terminal substituent group of the pyridinium plays a vital role in third-order NLO behavior.
Co-reporter:Dandan Li, Xiaohe Tian, Aidong Wang, Lijuan Guan, Jun Zheng, Fei Li, Shengli Li, Hongping Zhou, Jieying Wu and Yupeng Tian
Chemical Science 2016 vol. 7(Issue 3) pp:2257-2263
Publication Date(Web):21 Dec 2015
DOI:10.1039/C5SC03956H
Rational design of specific ratiometric viscosity probes with small molecular weight is a challenge in practical biotechnology applications. Herein two novel water-soluble, small-molecular ratiometric probes, bearing N-methyl benzothiazolium moiety (DSF and DBF), are designed for two-photon fluorescent imaging as a functional of local viscosity. The dye DSF, a light-up fluorescent probe, is sensitive to local viscosity and selectively stains nuclear DNA, which can be used to inspect asynchronous cells under confocal microscopy. While the dye DBF as a molecular rotor displays strong fluorescence enhancement in viscous media or binding to RNA. It exhibits dual absorption and emission as well, and only the red emission is markedly sensitive to viscosity changes, providing a ratiometric response and selectively imaging nucleolic and cytosolic RNA. Interestingly it is shown, for the first time, that the intracellular targeting and localization (DNA and RNA) of the two dyes are entirely realized simply by modifying the substituent attached to the benzothiazolium.
Co-reporter:Jingyun Tan, Yujin Zhang, Meirong Zhang, Xiaohe Tian, Yiming Wang, Shengli Li, Chuankui Wang, Hongping Zhou, Jiaxiang Yang, Yupeng Tian and Jieying Wu
Journal of Materials Chemistry A 2016 vol. 4(Issue 15) pp:3256-3267
Publication Date(Web):04 Mar 2016
DOI:10.1039/C6TC00382F
Designing small molecules with large two-photon absorption cross sections is urgently needed. In the present work, six novel chalcone thiophene derivatives were obtained by tuning the terminal electron-withdrawing/donating groups rationally. Their structure–property relationship was investigated both experimentally and theoretically. Crystallographic studies revealed that structural diversity was mainly influenced by ethyloxy groups. Both the alternation of electron-withdrawing/donating groups and the polarity of different solvents had a considerable influence on their photophysical properties. The results of UV-vis and one-/two-photon excited emission spectra showed that the high polarity solvents increased the quantum yields (Φ) and two-photon absorption cross-sections (σ) of type C chalcones, while they decreased those of type OC chalcones. It should be highlighted that as they are small molecules, favorable Φ and σ values were obtained. Finally, a preliminary attempt has been made in the biological imaging field, with satisfactory results that C-1 and OC-1 could locate uniformly in a cytosolic membrane-like system.
Co-reporter:Hui Wang, Xiaohe Tian, Lijuan Guan, Qiong Zhang, Shengyi Zhang, Hongping Zhou, Jieying Wu and Yupeng Tian
Journal of Materials Chemistry A 2016 vol. 4(Issue 17) pp:2895-2902
Publication Date(Web):01 Apr 2016
DOI:10.1039/C6TB00433D
As a semi-autonomous organelle, the eukaryotic mitochondrion possesses an individual DNA and protein synthesizing system. Therefore, the mitochondrial DNA-targeting probes are powerful tools to understand the functions in physiological processes. Herein, we report a novel Ru(II) complex (HLRu) based on a phenanthroline derivative to target mitochondrial DNA. The nonlinear optical property study revealed a reverse nonlinear optical refraction character from self-focusing to self-defocusing response before and after complexation with Ru(II). Furthermore, the two-photon absorption and high biocompatibility of complex HLRu highlight its potential applications in biological processes. It was found that complex HLRu specifically binds to mitochondrial DNA in living cells and enables imaging of tissues with minimal auto-fluorescence. As a result, this complex HLRu probe offers a promising platform to directly monitor mitochondrial DNA in living cells.
Co-reporter:Qiong Zhang, Xiaohe Tian, Zhangjun Hu, Caroline Brommesson, Jieying Wu, Hongping Zhou, Jiaxiang Yang, Zhaoqi Sun, Yupeng Tian, Kajsa Uvdal
Dyes and Pigments 2016 Volume 126() pp:286-295
Publication Date(Web):March 2016
DOI:10.1016/j.dyepig.2015.11.026
•A series of novel imidazole-pyrimidine derivatives (EX-1∼EX-4) were designed and confirmed by crystallography.•The photophysical properties were systematically investigated.•The 2PA cross-section values (σ) were obtained both by Z-Scan and 2PEF measurements.•EX-1 and EX-2 were identified to be the best candidates for living cells (HepG2) imaging.A series of novel D–π–A type two-photon absorption (2PA) imidazole-pyrimidine derivatives (EX-1∼EX-4) have been synthesized and characterized, with EX-1 was crystallography confirmed. Based on systematic photophysical investigations, the structure–property relationships can be drawn as follows: (1) Both theoretical and experimental studies indicated that the different donor groups have large influences on the optical properties. (2) The 2PA cross-section values (σ) were obtained both by Z-Scan and two-photon excited fluorescence (2PEF) measurements. 2PA cross sections show an increasing trend with increasing electron-donating strength and the number of branches. (3) Comprehensively considered the optical performance, molecular volume, cytotoxicity and solubility, EX-1 and EX-2 were identified to be the best candidates for living cells (HepG2) imaging. Moreover, the 2PA excitable features of EX-1 and EX-2 are capable of imaging in fresh mouse's liver tissues with a depth of ca. 70 μm.
Co-reporter:Jie Liu, Yingzhong Zhu, Xiaohe Tian, Fei Li, Wentao Xu, Yujin Zhang, Chuankui Wang, Jun Zhang, Hongping Zhou, Jieying Wu, Yupeng Tian
Dyes and Pigments 2016 Volume 128() pp:149-157
Publication Date(Web):May 2016
DOI:10.1016/j.dyepig.2015.10.040
•Photophysical properties were tuned by subtle substitute changes on host framework.•Crystallography structures of novel terpyridine derivatives were determined.•Two-photon absorption properties were studied both experimentally and theoretically.•Relationships between the structures and properties were investigated.•Applications in bioimaging for the terpyridine derivatives were carried out.Five novel 2, 2′:6′, 2″-terpyridine derivatives (L1-L5) with subtle substitute changes have been designed and synthesized. Their structures were determined by the single crystal X-ray diffraction analysis. It was observed that L1 and L2 containing an acceptor (–NO2) group exhibited three strong absorption bands, while L3, L4 and L5 containing donors (–OCH3/NH2) exhibited two absorption bands similar to that of ligand L0. Two-photon absorption cross sections were measured by two-photon excited fluorescence and open aperture Z-scan methods, respectively. Further, the two-photon absorption properties were explained by the hybrid density functional theory (DFT/B3LYP). The results indicated that L5 with amino group possessed the largest two-photon absorption cross-section values. The systematic investigations revealed that the linear/nonlinear optical properties could be tuned by subtle terminal unit changes for the Donor–Acceptor framework. Due to the existed –NH2 moiety, the subcellular acidic organelle targeting in living cells finally observed using such compounds under two-photon confocal microscopy.
Co-reporter:Qiong Zhang, Lei Luo, Hong Xu, Zhangjun Hu, Caroline Brommesson, Jieying Wu, Zhaoqi Sun, Yupeng Tian and Kajsa Uvdal
New Journal of Chemistry 2016 vol. 40(Issue 4) pp:3456-3463
Publication Date(Web):10 Feb 2016
DOI:10.1039/C5NJ02874D
Novel donor–π–acceptor (D–π–A) and donor–π–acceptor–π–donor (D–π–A–π–D) type pyrimidine imidazole derivatives with flexible ether chains (L1 and L2) have been efficiently synthesized through improved Knoevenagel condensation and Ullmann reactions with high yields. Based on systematic photophysical investigations and theoretical calculations, the structure–property relationships can be described as follows: (1) the linear and nonlinear optical properties of the target chromophores change regularly with increasing the number of branches and the polarity of the solvents. (2) The single-substituted chromophore L2 exhibited a remarkable negative solvato-kinetic effect, while the double-substituted chromophore L1 showed a positive solvato-kinetic effect. Significant bathochromic shifting of the emission spectra and larger Stokes shifts were observed in polar solvents. (3) The two-photon absorption (TPA) cross-section results further demonstrated that their TPA cross section values (δ) increase notably with increasing branch number, and the presence of high π-delocalization could induce large size-scalable TPA enhancements. (4) By comprehensively considering the optical performance, cytotoxicity and solubility, L1 was identified as the better candidate for living cell (HepG2) imaging.
Co-reporter:Jian Su, Liudi Yao, Jun Zhang, Shizhen Yuan, Fazhi Xie, Yi Ding, Meng Zhao, Shichao Wang, Hao Li, Shengyi Zhang, Jieying Wu and Yupeng Tian
New Journal of Chemistry 2016 vol. 40(Issue 1) pp:97-100
Publication Date(Web):17 Nov 2015
DOI:10.1039/C5NJ02144H
A novel M3L2 cage-based microporous coordination polymer assembled from the six-coordinated Cd(II) ion and a flexible tricarboxylic ligand has been designed and synthesized. The solvent-dependent luminescence properties revealed that the coordination polymer has an obvious, enhanced luminescence in the solvents CH2Cl2 and CHCl3.
Co-reporter:Yanan Shi, Lufei Xiao, Dajun Wu, Fei Li, Dandan Li, Jun Zhang, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian
Journal of Organometallic Chemistry 2016 Volume 817() pp:36-42
Publication Date(Web):15 August 2016
DOI:10.1016/j.jorganchem.2016.04.032
•Two novel ferrocene derivatives have been designed, synthesized and fully characterized.•The electrochemical properties of the two compounds were studied by cyclic voltammetric experiments.•The third-order nonlinear optical properties were investigated by Z-scan technique.Two novel ferrocene derivatives, N,N-diphenyl-4-E-((1-ferrocenyl) ethenyl) aniline (1), N,N-(4,4-diethoxyphenyl)-4-E-((1-ferrocenyl)ethenyl)aniline (2), were designed, synthesized and fully characterized by 1H NMR, 13C NMR, FT-IR and MALDI-TOF-MS spectra. Structure of (1) was confirmed by X-ray diffraction analysis. The UV–visible absorption spectra of the two compounds were investigated and verified by density functional theory (DFT) calculations. Electrochemical and third-order nonlinear optical (NLO) properties have been shown by cyclic voltammetric experiments and open/closed aperture Z-scan measurements. The results show that the two compounds both are highly π-electron delocalization system, indicating potential applications as NLO materials. It is noteworthy that (1) possesses larger two-photon absorption (2 PA) coefficient β, 2 PA cross section σ and the third-order nonlinear susceptibility (χ(3)) than (2).Two novel D1-π-D2 ferrocenyl compounds, (1) and (2), were designed, synthesized and fully characterized. They have potential applications as NLO materials and all-optical switching.
Co-reporter:Pengfei Shi, Qin Jiang, Qiong Zhang, Yupeng Tian
Journal of Organometallic Chemistry 2016 Volume 804() pp:66-72
Publication Date(Web):15 February 2016
DOI:10.1016/j.jorganchem.2015.12.017
•Terpyridines influenced the emission ability of their alkynylplatinum complexes.•Four alkynylplatinum terpyridine complexes are soluble in water.•Four alkynylplatinum complexes interacted with DNA in different modes.Four novel alkynylplatinum(II) terpyridine complexes, [Pt(CCPhR)L]Cl (L = (E)-4′-(4- N, N-bis(2-(2-methoxyethoxy)ethylamino)styrylphenyl)-2,2′:6′,2″-terpyridine (O4TPY) or 4′-p-N, N-bis(2-hydroxyethyl)aminobenzyl-2,2′:6′,2″-terpyridine (TPYOH) and R = n-Bu or H), were synthesized and characterized using 1H NMR, 13C NMR, MALDI-TOF-MS and elemental analysis. All Pt(II) complexes were weakly emissive at ambient temperature in a mixed solution of acetonitrile and water, in which two alkynylplatinum(II) complexes of TPYOH showed much longer emission maximum than those of O4TPY (677 nm for [Pt(CCPh) (TPYOH)]Cl vs 581 nm for [Pt(CCPh) (O4TPY)]Cl and 689 nm for [Pt(CCPhBu) (TPYOH)]Cl vs 595 nm for [Pt(CCPhBu) (O4TPY)]Cl). UV–vis titration experiments indicated that only two alkynylplatinum(II) complexes of O4TPY can bind CT-DNA and the binding constant Kb was 1.9 × 105 for [Pt(CCPh) (O4TPY)]Cl and 1.1 × 105 for [Pt(CCPhBu) (O4TPY)]Cl, respectively. The circular dichroism results indicted that the complexes [Pt(CCPhR) (O4TPY)]Cl can change the helicity of DNA, while the complexes [Pt(CCPhR) (TPYOH)]Cl could interact with the DNA base pair. The influence of ligands in the four complexes on their emission and DNA binding properties were discussed.The four alkynylplatinum(II) terpyridyl complexes were emissive from 3MLCT excited state at ambient temperature in solution. The cations in the four complexes showed different interactions with ct-DNA.
Co-reporter:Dandan Li, Yanan Shi, Xiaohe Tian, Mingming Wang, Bei Huang, Fei Li, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian
Sensors and Actuators B: Chemical 2016 Volume 233() pp:1-6
Publication Date(Web):5 October 2016
DOI:10.1016/j.snb.2016.03.167
•DB1 and DB2 show rapid response, high selectivity and sensitivity for bisulfite/sulfite anions with significant ratiometric fluorescent signal changes.•The detection limit was determined to be 0.16 μM for DB1 and 0.57 μM for DB2, respectively, which is sufficient to probe the HSO3− concentration in cells.•DB1 and DB2 were successfully applied for bioimaging SO2 derivatives in living cells under one- and two-photon confocal microscopy.The development of rapid, convenient, and sensitive methods for selective detection SO2 derivatives is of considerable significance in biomedical research and has become a topical objective. Herein four probes (DS1, DS2, DB1 and DB2) based on π-conjugated indolium/benzoindolium systems were designed for detection bisulfite/sulfite. The results indicated that probes DB1 and DB2 showed rapid response, high selectivity and sensitivity for bisulfite/sulfite anions with significant ratiometric fluorescent signal changes. Moreover, DB1 and DB2 were successfully applied for bioimaging SO2 derivatives in living cells under one- and two-photon confocal laser scanning microscopy. This paradigm provided a promising methodology for the design of ratiometric and two-photon bisulfite/sulfite sensors.Two ratiometric probes for rapid and colorimetric detection of HSO3−/SO32− anionswere developed. The probes were based on π-conjugated indolium/benzoindolium systems, in which the nucleophilic attack of HSO3−/SO32− interrupted the π-conjugation and blocked the ICT process, resulting in significant ratiometric optical signal changes and two-photon fluorescent ‘turn-off’ effect. The detection limit was determined to be 0.16 μM for DB1 and 0.57 μM for DB2, respectively, which was sufficient to probe the HSO3− concentration in cells. In addition, the sensing mechanism was well rationalized with the aid of TD-DFT calculations. Moreover, DB1 and DB2 were successfully applied for bioimaging SO2 derivatives in living cells under one- and two-photon confocal microscopy. We expected that this paradigm can provide a promising methodology for the design of ratiometric and two-photon bisulfite/sulfite sensors. More broadly, the ratiometric and two-photon probes will be of great benefit to biomedical researchers studying SO2 derivatives in biological systems.
Co-reporter:Xiaohe Tian;Hui Wang;Lijuan Guan;Qiong Zhang;Hongping Zhou
Journal of Fluorescence 2016 Volume 26( Issue 1) pp:59-65
Publication Date(Web):2016 January
DOI:10.1007/s10895-015-1703-1
In this letter, aggregation from two-photon absorption (2PA) molecules in living cells were firstly observed and the related aggregation induced emission (AIE) properties were investigated as a cell tracer for L ((Z)-3-(4-(Bis(4-ethoxyphenyl) amino)phenyl)-2-(4-amino-phenyl)- acrylonitrile cyano-substituted ) based on triphenylamine with D–π–A model. L was further used as a two-photon absorption (2PA, λex = 900, λem = 550 nm δ = 156 GM) live-cell marker for real-time, long-term cell growth and proliferation monitoring, with rapidly adhering whole intracellular membrane-rich system. Remarkably, different from existing organic AIE chromophores and other commercially available probes, L exhibited intense intracellular-AIE property with stable nuclear envelope (NE) staining under two-photon excited microscopy (TPEM) through detailed in cellulo studies.
Co-reporter:Qiong Zhang, Xiaohe Tian, Hui Wang, Zhangjun Hu, Jieying Wu, Hongping Zhou, Shengyi Zhang, Jiaxiang Yang, Zhaoqi Sun, Yupeng Tian, Kajsa Uvdal
Sensors and Actuators B: Chemical 2016 Volume 222() pp:574-578
Publication Date(Web):January 2016
DOI:10.1016/j.snb.2015.08.079
•Two new two photon chemosensors CCP and COP were synthesized and fully characterized.•They show strong fluorescence quenching and good ratiometric responses.•The two-photon fluorescence intensity could be effectively enhanced on adding EDTA.•The internalization (CCP → Fe3+, COP → Cu2+) with cells and shows the “light switch” property.Two novel NIR-region two-photon fluorescent probes CCP and COP, show strong fluorescence quenching and good ratiometric responses toward Fe3+ and Cu2+, respectively; and their two-photon fluorescence are reversible by the subsequent addition of EDTA. CCP and COP are valuable candidates for two-photon imaging in the biological transparency window.
Co-reporter:Qiong Zhang, Xiaohe Tian, Zhangjun Hu, Caroline Brommesson, Jieying Wu, Hongping Zhou, Shengli Li, Jiaxiang Yang, Zhaoqi Sun, Yupeng Tian and Kajsa Uvdal
Journal of Materials Chemistry A 2015 vol. 3(Issue 36) pp:7213-7221
Publication Date(Web):06 Aug 2015
DOI:10.1039/C5TB01185J
It is still a challenge to obtain two-photon excited fluorescent bioimaging probes with intense emission, high photo-stability and low cytotoxicity. In the present work, four Zn(II)-coordinated complexes (1–4) constructed from two novel D–A and D–π–A ligands (L1 and L2) are investigated both experimentally and theoretically, aiming to explore efficient two-photon probes for bioimaging. Molecular geometry optimization used for theoretical calculations is achieved using the crystallographic data. Notably, the results indicate that complexes 1 and 2 display enhanced two-photon absorption (2PA) cross sections compared to their corresponding D–A ligand (L1). Furthermore, it was found that complex 1 has the advantages of moderate 2PA cross section in the near-infrared region, longer fluorescence lifetime, higher quantum yield, good biocompatibility and enhanced two-photon excited fluorescence. Therefore, complex 1 is evaluated as a bioimaging probe for in vitro imaging of HepG2 cells, in which it is observed under a two-photon scanning microscope that complex 1 exhibits effective co-staining with endoplasmic reticulum (ER) and nuclear membrane; as well as for in vivo imaging of zebrafish larva, in which it is observed that complex 1 exhibits specificity in the intestinal system.
Co-reporter:Ming Kong, Ting Wang, Xiaohe Tian, Fang Wang, Yanqiu Liu, Qiong Zhang, Hui Wang, Hongping Zhou, Jieying Wu and Yupeng Tian
Journal of Materials Chemistry A 2015 vol. 3(Issue 21) pp:5580-5588
Publication Date(Web):20 Apr 2015
DOI:10.1039/C5TC00716J
A series of asymmetrical D–π–D type thiophene-based chromophores with small sizes and different electron-donating groups were designed and synthesized in high yield. Single-crystal X-ray diffraction analysis and theoretical calculations were carried out to further explore the electronic structural features of the chromophores. It was observed that multiple C–H⋯π interactions and C–H⋯O hydrogen bonds played an important role in crystal stacking. Systematic investigations, including fluorescence quantum yields, fluorescence lifetime, and two-photon absorption (2PA) cross sections, revealed that the photophysical properties of the thiophene-based chromophores can be tunable by the modulation of electron-donating terminal units. Furthermore, by introducing a carbonyl group in the π-bridge center, one of the chromophores with a small size exhibited significantly enhanced two-photon absorption with a 36-fold increase of the 2PA cross section compared with that of the corresponding chromophore. Finally, due to their superior 2PA character in the near-infrared region (700–900 nm), two-photon excited bioimaging applications were carried out for the chromophores. The results of live cell imaging experiments showed that the chromophores can be effectively penetrated into the cytosol of HepG2 cells and their physiological activity can be detected in vitro using two-photon fluorescence microscopy.
Co-reporter:Lin Kong, Yu-peng Tian, Qi-yu Chen, Qiong Zhang, Hui Wang, Dong-qin Tan, Zhao-ming Xue, Jie-ying Wu, Hong-ping Zhou and Jia-xiang Yang
Journal of Materials Chemistry A 2015 vol. 3(Issue 3) pp:570-581
Publication Date(Web):05 Nov 2014
DOI:10.1039/C4TC01605J
A D–π–A type triphenylamine derivative (E)-3-(4-(4-(diphenylamino)styryl)-phenyl)acrylonitrile (abbreviated as L) is designed, synthesized and characterized by single crystal X-ray diffraction analysis, which is demonstrated to exhibit superior AIEE (aggregation-induced enhanced emission) properties. Self-aggregates of L obtained with and without the guidance of metal ions (Cd2+ or Cu2+) showed morphology-dependent luminescent properties. The coupling and synergy effects between L and metal ions bring about an energy transfer process between the components, which further results in red-shifted absorption and fluorescence, an enhanced fluorescent quantum yield and tunable FL lifetime. The interactions between L and metal ions also change nonlinear optical properties, including two-photon excited fluorescence (2PEF), two-photon absorption (2PA) cross-section (δ), two-photon action cross-section (ηδ) and two-photon absorption coefficient (β), which further leads to successful application of the samples as a two-photon fluorescent probe for labelling the intercellular section. The study indicates that the preparation of nanohybrids from metal ions and an AIEE organic compound is a promising method to prepare 2PA probes possessing a high ηδ for biological imaging.
Co-reporter:Jian Su, Liudi Yao, Meng Zhao, Hui Wang, Qiong Zhang, Longjiu Cheng, Jun Zhang, Shengyi Zhang, Jieying Wu, and Yupeng Tian
Inorganic Chemistry 2015 Volume 54(Issue 13) pp:6169-6175
Publication Date(Web):June 5, 2015
DOI:10.1021/acs.inorgchem.5b00180
It is still an enormous challenge to obtain the metal–organic frameworks (MOFs) with specific properties by tuning their structures. Here we first reported that the structures of MOFs could be tuned by adding certain amount of zwitterion pyridiniumolate. To demonstrate the inductive effect, two series of assembly experiments were performed using different metal ions, namely, Cd(II) and Mn(II). The experimental results revealed that the zwitterion pyridiniumloate only acted as a structural induction agent (SIA), which did not exist in the aimed compounds. The SIAs could effectively tune the framework aperture or promote coordination and further tune the properties of MOFs without any removal or exchange after the synthesis. Therefore, the results could not only immensely expand the syntheses and structural diversity of MOFs with the fixed metal ions and organic ligands but also afford the possibility and effective convenience for tuning the properties of MOFs in the functional material research fields.
Co-reporter:Rui Ke, Xiaomei Zhang, Shengyi Zhang, Shengli Li, Changjie Mao, Helin Niu, Jiming Song and Yupeng Tian
Physical Chemistry Chemical Physics 2015 vol. 17(Issue 41) pp:27548-27557
Publication Date(Web):22 Sep 2015
DOI:10.1039/C5CP04419G
A facile one-step method for the synthesis of a water-soluble selenium/polypyrrole (Se/PPy) nanocomposite was developed. In the aqueous synthesis process, the pyrrole acted as a reductant for the reduction of H2SeO3, and then the elemental Se formed in situ acted as a catalyst for the polymerization of pyrrole. The characterization results show that the as-obtained composite (Se/PPy) is a spherical (Φ80 nm) product that is made up of amorphous Se particles coated by PPy layers. The formation mechanism and influence factors of the products were discussed, based on a series of experiments. It is proposed that remainder H2SeO3 adsorbed on the PPy chains increased the water-solubility and conductivity of the Se/PPy nanocomposite. Significantly, relying on the synergistic effect of photo-conductive Se nanoparticles and electric-conductive PPy molecules, the Se/PPy nanocomposite possesses a large two-photon absorption (2PA) cross-section and good optical limiting properties, which were demonstrated by the Z-scan technique using a femtosecond laser. We believe that this work should be an interesting strategy for developing polymer composites with excellent optoelectrical properties.
Co-reporter:Zhaodi Liu, Fuying Hao, Huajie Xu, Hui Wang, Jieying Wu and Yupeng Tian
CrystEngComm 2015 vol. 17(Issue 29) pp:5562-5568
Publication Date(Web):08 Jun 2015
DOI:10.1039/C5CE00816F
Three different pyridinium salts with I−, BPh4− or [Eu(TTA)4]− anions were synthesized and fully characterized. The crystal structures and 1H-NMR spectra of the dipyridinium cations showed that the coplanarity of the cation was controlled by the type of anion. Their one- and two-photon absorption properties were studied in combination with their structure. The two-photon absorption properties were shown to be tunable by the counter-anions. A pyridinium salt containing L[Eu(TTA)4]2 was selected as a marker for use in fluorescence microscopy to image living cells. This salt clearly displayed the cell structure and was used successfully in two-photon excited fluorescence microscopy.
Co-reporter:Jingyun Tan, Rui Li, Dandan Li, Qiong Zhang, Shengli Li, Hongping Zhou, Jiaxiang Yang, Jieying Wu and Yupeng Tian
Dalton Transactions 2015 vol. 44(Issue 3) pp:1473-1482
Publication Date(Web):12 Nov 2014
DOI:10.1039/C4DT02933J
A novel 4′-(4-(diphenylamino)thienyl)-2,2′:6′,2′′-terpyridine ligand (L) based on thiophene and its LZnX2 complexes (X = Cl, Br, I, SCN) was designed, synthesized and characterized by elemental analysis, far-IR, MALDI-TOF-MS, and single crystal X-ray diffraction analysis. Structural studies revealed that the central zinc(II) atom adopted a distorted trigonal bipyramidal coordination model. However, there were different hydrogen bonds and stacking models with different counter anions in the crystals. The absorption properties of the compounds were investigated with the aid of TD-DFT computational methods. Furthermore, the third-order nonlinear optical (NLO) properties were systematically studied via open-aperture Z-scan methods using a tunable wavelength femtosecond laser. The results from photophysical property investigations suggested that the complexation of the thiophene-based terpyridine ligand with zinc halides resulted in strong ICT/LLCT bands of about 450 nm, and the complexes exhibited strong nonlinear optical response in the near-infrared range around 850 nm. Above all, the two-photon absorption (2PA) cross-section values (σ) were enhanced by coordination with zinc and influenced by halide ions, reaching up to 2583 GM (X = Br).
Co-reporter:Pengfei Shi, Qin Jiang, Xuesong Zhao, Qiong Zhang and Yupeng Tian
Dalton Transactions 2015 vol. 44(Issue 17) pp:8041-8048
Publication Date(Web):19 Mar 2015
DOI:10.1039/C5DT00449G
Two water soluble 2,2′:6′,2′′-terpyridine derivatives (TPYOH and O3TPY) with a di(hydroxyethyl)amino or a long (2-(2-methoxyethoxy)ethoxy)benzyl group, respectively, were designed and synthesized. The two terpyridine ligands and their Zn(II) complexes display strong one-photon fluorescence. An unusually large solvatochromism effect in ethanol and water was found, which was ascribed to their interactions with the solvent through hydrogen bonds. All the four compounds show evident two-photon absorption ability when evaluated by Z-scan technology. The free ligands could give distinct two-photon excited fluorescence, and the emission of O3TPY responded linearly with Zn2+ under the excitation of a 780 nm femtosecond laser. Only the complex ZnO3TPY, which possesses a large π conjugation system and suitable election-donating groups, displayed emission maxima at 595 nm when excited by a 680–880 nm laser.
Co-reporter:Pengfei Shi, Qin Jiang, Sergio Sánchez, Xuesong Zhao, Qiong Zhang and Yupeng Tian
Dalton Transactions 2015 vol. 44(Issue 30) pp:13760-13760
Publication Date(Web):07 Jul 2015
DOI:10.1039/C5DT90118A
Correction for ‘Study of the one-photon and two-photon properties of two water-soluble terpyridines and their zinc complexes’ by Pengfei Shi et al., Dalton Trans., 2015, 44, 8041–8048.
Co-reporter:Xuesong Zhao, Jie Liu, Hui Wang, Yan Zou, Shengli Li, Shengyi Zhang, Hongping Zhou, Jieying Wu and Yupeng Tian
Dalton Transactions 2015 vol. 44(Issue 2) pp:701-709
Publication Date(Web):03 Nov 2014
DOI:10.1039/C4DT02251C
Three novel organooxotin complexes (Z1, Z2 and Z3) were synthesized by reaction of L1 (2-cyano-3-(4-(diphenylamino)phenyl) acrylic acid) with n-Bu2SnO, Ph3Sn(OH) and nBu6Sn2O. The structures of the three complexes have been confirmed by single-crystal X-ray diffraction analysis. The metal complex Z1 features a ladder framework while Z2 and Z3 show discrete structures. The UV-vis absorption, single-photon excited fluorescence (SPEF) and two-photon excited fluorescence (2PEF) of the complexes have been systematically studied, suggesting that the three metal complexes have strong two-photon absorption (2PA) and large 2PA cross-sections. It is noteworthy that Z2 possesses an enhanced two-photon absorption, and Z3 exhibits larger 2PA cross-section per molecular weight compared to L1. Finally, high anti-tumor activity of these three metal complexes has also been identified.
Co-reporter:Lufei Xiao, Hui Wang, Qiong Zhang, Yingzhong Zhu, Junshan Luo, Yunke Liang, Shengyi Zhang, Hongping Zhou, Yupeng Tian, Jieying Wu
Dyes and Pigments 2015 Volume 113() pp:165-173
Publication Date(Web):February 2015
DOI:10.1016/j.dyepig.2014.08.002
•Five novel Ru (II) polypyridyl complexes were synthesized and fully characterized.•The photophysical properties of them were systematically investigated.•The complexes all display excellent third-order NLO properties.•The σ of cyclometalated complexes are larger than that of noncyclometalated ones.•The five complexes are all intercalation model with DNA.Five novel ruthenium (II) polypyridyl (N∧N∧N or N∧N∧C) complexes (1–5) containing carbazole with flexible substituents have been synthesized, and fully characterized. The crystal structure of complex 5 was determined by X-ray diffraction analysis. The photophysical properties of them were systematic studied. The complexes exhibited ligand-centered π–π∗ transition in the range of 290–350 nm and metal-to-ligand charge transition bands in the range of 450–650 nm. The third-order nonlinear optical response was measured by Z-scan technique for the complexes. The results revealed that cyclometalated (N∧N∧C) complexes 1 and 2 possess a stronger third-order nonlinear optical response than those of noncyclometalated (N∧N∧N) complexes 3, 4 and 5. The DNA binding behaviors of the complexes have been investigated by spectroscopic and viscosity measurements. It was found that the complexes can interact with DNA in different modes, including classical intercalation for complexes 1–3 and partial intercalation for complexes 4–5.Five novel Ru (II) polypyridyl complexes have been synthesized and their third-order nonlinear optical properties and DNA-binding behaviors have been systematically studied.
Co-reporter:Qiong Zhang, Xiaohe Tian, Guiju Hu, Pengfei Shi, Jieying Wu, Shengli Li, Hongping Zhou, Bao-Kang Jin, Jiaxiang Yang, Shengyi Zhang, and Yupeng Tian
Biochemistry 2015 Volume 54(Issue 13) pp:2177-2180
Publication Date(Web):February 4, 2015
DOI:10.1021/bi5014062
Here we have designed and synthesized a novel analogous cis-platinum complex (TDPt) with strong two-photon absorption properties and higher stability upon laser irradiation. Interestingly, a higher cytotoxicity against three types of cancer cells compared to that of commercial cis-platinum was observed. The initial confocal micrographs showed that lysosomes may be the biological targets of such TDPt, except the conventional presumed DNA. This hypothesis was further confirmed by the two-photon microscopy and transmission electron microscopy micrograph. These results form an important basis for future “on-site observation” of the anticancer mechanism of the Pt(II) complex.
Co-reporter:Wan Sun, Yingzhong Zhu, Anran Wang, Lin Kong, Shengli Li, Jieying Wu and Yupeng Tian
New Journal of Chemistry 2015 vol. 39(Issue 9) pp:6830-6835
Publication Date(Web):09 Jun 2015
DOI:10.1039/C5NJ00587F
The third-order nonlinear materials have been the focus of present research. It is known that the χ(3) value of the organic optical material is generally small, and hardly displays any evident third order nonlinear effect. However, the χ(3) value was significantly improved when the organic ligands were combined with nano-Ag due to the increase of surface plasmon resonance. The nano-Ag changes its local electric field, and in turn causes a regional interaction between the ligand and the metal clusters. In this article, a new optical carbazole derivative (E)-2-(4-([2,2′:6′,2′′-terpyridine]-4′-yl)styryl)-9-hexyl-9H-carbazole, abbreviated as L, has been designed and synthesized. The ligands were combined with nano-Ag, acting on the surface and stabilizing the system without any extra control such as surfactant and pH, which may be explained by the theory of hard and soft acid–base. Careful characterizations have been performed by UV-vis absorption spectroscopy, 1H NMR spectroscopy, FT-IR, XRD and TEM. Particular properties have been shown by fluorescence spectra, fluorescence lifetime, Raman spectrum, non-linear optical response and cyclic voltammetry curve. The results indicate that the nano-composite L–Ag NCs have a stronger Raman enhancement effect, shorter fluorescence lifetime and larger two-photon absorption (TPA) when compared to the free ligand L. The data for the TPA cross-section value (σ = 1336.85 GM), nonlinear refractive index (γ = 2.23 × 10−13 cm2 W−1) and third order nonlinear optical susceptibility (Re(χ(3)) = 1.16 × 10−11 esu) are measured and discussed.
Co-reporter:Lufei Xiao, Liuyang Zhu, Qinglong Zeng, Qishi Liu, Jun Zhang, Shengli Li, Hongping Zhou, Shengyi Zhang, Jieying Wu, Yupeng Tian
Journal of Organometallic Chemistry 2015 s 789–790() pp: 22-28
Publication Date(Web):1 August 2015
DOI:10.1016/j.jorganchem.2015.05.007
•One novel ligand, 4′-ferrocenyl-4, 2′: 6′, 4″-terpyridine, have been designed and synthesized.•Five novel metal-organic hybrid materials have been prepared by self-assembly method.•The structural features of the ligand and the five complexes have been systematic investigated.•The optical band gaps of the ligand and the five complexes have been confirmed by the diffuse reflectance spectra.Five novel Zinc (II) metal-organic hybrid materials, [(ZnCl2L)6·6(H2O)·6(CHCl3)] (1), [(ZnBr2L)6·6(H2O)·6(CHCl3)] (2), [ZnI2L·2(CHCl3)]n(3), [Zn(SCN)2L·(CHCl3)]n(4), and [Zn(CHCOO)2L·2(H2O)]n(5), have been assembled by a novel ligand 4′-ferrocenyl-4, 2′: 6′, 4″-terpyridine and different zinc salts under ambient conditions, and their structures have been confirmed by single-crystal X-ray diffraction analysis. The results indicate that both complexes 1 and 2 adopt a metallohexacycle consisting of six ligands and six zinc ions, and complexes 3, 4 and 5 are all one-dimensional polymers. The supramolecular frameworks are constructed by complexes 1–5 through the C–H⋯X (X = Cl, Br, I, S, O or π) or π–π intermolecular interactions. In addition, the optical band gaps were confirmed by use of the optical diffuse reflectance spectra, and the results show that the ligand and complexes 1–5 should have semiconductor properties.Five novel metal-organic hybrid materials have been prepared by self-assembly method, and their structural features were systematic investigated.
Co-reporter:Dandan Li, Qiong Zhang, Xuchun Wang, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian
Dyes and Pigments 2015 120() pp: 175-183
Publication Date(Web):
DOI:10.1016/j.dyepig.2015.03.039
Co-reporter:Dandan Li, Xianshun Sun, Nanqi Shao, Guocui Zhang, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian
Polyhedron 2015 Volume 93() pp:17-22
Publication Date(Web):17 June 2015
DOI:10.1016/j.poly.2015.03.027
A series of novel metal complexes, [Cu2(dppm)2(OOCL)]2[NO3]2 (1), [Ag2(dppm)2(OOCL)2] (2) and [Au2(dppm)2(OOCL)2] (3) (dppm = bis(diphenylphosphino)methane, L = 2-cyano-3-(4-(diphenylamino) phenyl)acrylic acid) were prepared and structurally characterized by X-ray crystallography. Their optical properties were investigated by absorption and fluorescence spectra. The fluorescence spectra of the complexes showed red shifts relative to that of L, which exhibited the same tendency as the absorption spectra. In addition, the ability of 1–3 to generate electrochemiluminescence (ECL) were assessed in acetonitrile solutions, they exhibited a highly enhanced stable ECL emission compared to the free ligand (L). Especially, the ECL intensity of 1 was approximately 30 times greater than that of L.1–3 exhibited a highly enhanced stable ECL emission compared to L. Especially, the ECL intensity of 1 is approximately 30 times greater than that of L. This implies that the introduction of heavy metals strengthens the spin–orbit coupling effect, improves the luminous efficiency of the materials and then enhances the ECL emission.
Co-reporter:Wei Du, Yingzhong Zhu, Hui Wang, Xuesong Zhao, Jieying Wu, Yupeng Tian
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2015 Volume 136(Part C) pp:1807-1815
Publication Date(Web):5 February 2015
DOI:10.1016/j.saa.2014.10.089
Co-reporter:Ming Kong, Yanqiu Liu, Hui Wang, Junshan Luo, Dandan Li, Shengyi Zhang, Shengli Li, Jieying Wu, Yupeng Tian
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2015 Volume 135() pp:521-528
Publication Date(Web):25 January 2015
DOI:10.1016/j.saa.2014.07.039
•Four Zn(II) terpyridine complexes with different coordination anions were designed and synthesized.•The linear and nonlinear spectroscopic properties were carried out.•The results revealed that two Zn(II) complexes possessed larger TPA cross-sections.•The complex of ZnLCl2 showed superior optical power limiting property.Four novel Zn(II) terpyridine complexes (ZnLCl2, ZnLBr2, ZnLI2, ZnL(SCN)2) based on carbazole derivative group were designed, synthesized and fully characterized. Their photophysical properties including absorption and one-photon excited fluorescence, two-photon absorption (TPA) and optical power limiting (OPL) were further investigated systematically and interpreted on the basis of theoretical calculations (TD-DFT). The influences of different solvents on the absorption and One-Photon Excited Fluorescence (OPEF) spectral behavior, quantum yields and the lifetime of the chromophores have been investigated in detail. The third-order nonlinear optical (NLO) properties were investigated by open/closed aperture Z-scan measurements using femtosecond pulse laser in the range from 680 to 1080 nm. These results revealed that ZnLCl2 and ZnLBr2 exhibited strong two-photon absorption and ZnLCl2 showed superior optical power limiting property.Graphical abstractFour novel Zn(II) terpyridine complexes (ZnLCl2, ZnLBr2, ZnLI2, ZnL(SCN)2) based on carbazole derivative group were designed, synthesized and fully characterized. Their photophysical properties including absorption and one-photon excited fluorescence, two-photon absorption (TPA) and optical power limiting (OPL) were further investigated systematically and interpreted on the basis of theoretical calculations (TD-DFT). The results of NLO determination revealed that two Zn(II) complexes possessed larger two-photon absorption cross-sections and ZnLCl2 complex showed superior optical power limiting property which suggested a large polarizability, meeting the requirements for third-order NLO materials offering promise for applications in optical limiting in the near infrared region.
Co-reporter:Fei Li, Imad Elddin Haj Elhussin, Shengli Li, Hongping Zhou, Jieying Wu, and Yupeng Tian
The Journal of Organic Chemistry 2015 Volume 80(Issue 21) pp:10605-10610
Publication Date(Web):October 12, 2015
DOI:10.1021/acs.joc.5b01725
Direct coupling of indoles with C60 has been achieved for the first time. Transition-metal-free KOtBu-mediated reaction of indoles to [60]fullerene has been developed as a practical and efficient method for the synthesis of various 1,2-(3-indole)(hydro)[60]fullerenes that are otherwise difficult to direct synthesize in an efficient and selective manner. This methodology tolerates sensitive functionalities such as chloro, ester, and nitro on indole and builds molecular complexity rapidly, with most reactions reaching completion in <1 h. A plausible reaction mechanism is proposed to explain the high regioselectivity at the 3-position of the indoles and the formation of 1,2-(3-indole)(hydro)[60]fullerenes.
Co-reporter:Yanqiu Liu, Ming Kong, Qiong Zhang, Zhiwen Zhang, Hongping Zhou, Shengyi Zhang, Shengli Li, Jieying Wu and Yupeng Tian
Journal of Materials Chemistry A 2014 vol. 2(Issue 33) pp:5430-5440
Publication Date(Web):15 Jul 2014
DOI:10.1039/C4TB00464G
A specific series of D–π–A (1A–3A) and D–π–A (1B–3B) structural chromophores with various electron donors and π-conjugated bridges were designed, synthesized, and fully characterized. Their crystal structures were determined by single crystal X-ray diffraction analysis. The one/two-photon absorption properties of the chromophores have been successfully tuned by using different electron donors and π-bridges. Interestingly, it was found that chromophore 3B shows quite weak fluorescence in pure DMSO, while a significant AIE (aggregation-induced emission) effect is observed in water–DMSO (v/v 90%) mixtures with a sharp increase in fluorescence intensity of about 11 times. Furthermore, chromophore 3B shows strong two-photon excited fluorescence (TPEF) and has a large 2PA action cross-section (394 GM). The results of live-cell imaging experiments show that 3B can be effectively used as a bio-imaging probe in two-photon fluorescence microscopy towards HepG2 cells in vitro. The TPEF images of 3B not only exhibit cellular cytosol uptake but also exhibit actin regulatory protein uptake which are different from OPEF images.
Co-reporter:Cuiyun Nie, Qiong Zhang, Hongjuan Ding, Bei Huang, Xinyan Wang, Xianghua Zhao, Shengli Li, Hongping Zhou, Jieying Wu and Yupeng Tian
Dalton Transactions 2014 vol. 43(Issue 2) pp:599-608
Publication Date(Web):24 Sep 2013
DOI:10.1039/C3DT51318A
To explore the photophysical properties of coordination compounds with enhanced two-photon absorption, two novel six-coordinated metal complexes (ML2, M = Cd(II), Zn(II)) from carbazole β-diketone ligand (HL = 4,4,4-trifluoro-1-(9-butylcarbazole-3-yl)-1,3-butanedione) were prepared and fully characterized. Their crystal structures were determined by X-ray diffraction analysis. Both variable temperature 1H NMR spectra and MALDI-TOF mass spectrometry proved that the coordination compounds exhibit good stability in solution. The results of time-dependent density functional theory (TD-DFT) calculations indicated that the complexation of the ligands with metal ion extends the electronic delocalization in the coordination compounds, leading to enhanced two-photon absorption. The photophysical properties for the coordination compounds were identified relying on both experimentally and theoretically studies. Finally, confocal microscopy and two-photon microscopy fluorescent imaging of HepG2 cells labeled with the Zn(II) complexe revealed its potential applications as a biological fluorescent probe.
Co-reporter:Ban-Feng Ruan, Ying-Zhong Zhu, Wan-Ding Liu, Bao-An Song, Yu-Peng Tian
European Journal of Medicinal Chemistry 2014 Volume 72() pp:46-51
Publication Date(Web):24 January 2014
DOI:10.1016/j.ejmech.2013.10.064
•A bis(pyrazolyl)methane ligand and its ZnII complexes have been characterized by single X-ray diffraction.•1 is a binuclear ZnII complex.•Complex 1 displayed the most potent antibacterial activity against Pseudomonas putida.Three novel Zn(II) complexes (1–3) with 1,1′-(anthracen-9-ylmethylene)bis(1H-pyrazole) (L2) have been prepared and structurally characterized by X-ray crystallography. Among them, 1 is a binuclear Zn(II) complex while 2 and 3 are mononuclear. The in vitro cytotoxic and antibacterial activities of these complexes were also evaluated. The three complexes exhibit cytotoxic specificity and significant antitumor activity. The MIC50 value of complex 1 against Pseudomonas putida reaching 0.011 μg/mL much lower than that the positive control chloromycin (0.182 μg/mL), indicates that complex 1 is a potent antibacterial agent.Three novel Zn(II) complexes with 1,1′-(anthracen-9-ylmethylene)bis(1H-pyrazole) have been prepared and characterized by X-ray crystallography. Among them, 1 is a binuclear Zn(II) complex and exhibits strong antibacterial activity against Pseudomonas putida.
Co-reporter:Ruilong Zhang, Qiong Zhang, Zhaodi Liu, Longmei Yang, Jieying Wu, Hongping Zhou, Jiaxiang Yang and Yupeng Tian
CrystEngComm 2014 vol. 16(Issue 10) pp:2039-2044
Publication Date(Web):03 Dec 2013
DOI:10.1039/C3CE42069H
A styryl-pyridine derivative, 2,5-dibutoxy-1,4-bis[2-(4-pyridyl)ethenyl]benzene (L), has been designed and synthesised. Two polymorphs of L and crystals of [Zn(phen)3]2L(ClO4)4 were obtained by different crystallisation conditions. Polymorph-α was prepared by a solvent evaporation method. However, polymorph-β and a cocrystal of [Zn(phen)3]2L(ClO4)4 were obtained by different inducing reagents. It has been found that there are, in total, four independent conformations of the molecule L in the three kinds of crystals. We have calculated the standard molar enthalpy of formation (ΔHm) of each conformation and demonstrated that the stabilisation energy of each conformation significantly relies on both the planarity of the molecules (L) and bond length of conjugated bridges. Furthermore, the photophysical properties of the three kinds of crystals also exhibit differences in the vibration and absorption spectroscopies, solid-state photoluminescence and time-resolved fluorescence, which may arise from the chromophore's stacking modes and the intermolecular electronic interactions in the crystals. These results revealed that the optical properties of functional organic materials could be tuned by controlling their crystallisation environment for a specific molecule.
Co-reporter:Hui Wang, Qiong Zhang, Jun Zhang, Lin Li, Qian Zhang, Shengli Li, Shengyi Zhang, Jieying Wu, Yupeng Tian
Dyes and Pigments 2014 Volume 102() pp:263-272
Publication Date(Web):March 2014
DOI:10.1016/j.dyepig.2013.11.013
•The molecular geometry optimization is based on crystal data.•The photophysical properties of them were systematically investigated.•The two-photon cross-sections were measured by two-photon excitation fluorescent and Z-scan methods.•The di- and hexa-branched pyrimidine derivatives exhibit large two-photon cross-section in 800–890 nm regions in DMF solution.•The potential application of the di-branched chromophores in two-photon biological imaging was evaluated.A series of mono-, di- and hexa-branched pyrimidine derivatives possessing two-photon absorption have been synthesized. The spectral features of the dyes showed solvatochromic with significant bathochromic shifting of the emission spectra and large Stokes shifts in more polar solvents mainly due to the intramolecular charge-transfer. The two-photon absorption cross-section values were measured by two-photon excited fluorescence and open aperture Z-scan methods. The results revealed that the two-photon absorption cross-section values were enhanced with increasing electron-donating strength of the end group and branch number. The photophysical properties of the dyes were further investigated with the aid of theoretical calculations. In addition, the di-branched dyes has the largest values of two-photon absorption cross-section per molecular weight, low cytotoxicity and can be internalized by human liver cancer cell line and accumulates in the cytoplasm, allowing for live cell two-photon fluorescence imaging, so it is promising for in vitro and vivo cellular imaging applications.
Co-reporter:Dandan Li, Qiong Zhang, Xianshun Sun, Nanqi Shao, Rui Li, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian
Dyes and Pigments 2014 Volume 102() pp:79-87
Publication Date(Web):March 2014
DOI:10.1016/j.dyepig.2013.10.028
•A novel series of two-photon absorptivity hydrosoluble salts have been synthesized.•The molecular geometry optimization for calculation results from the structure information.•The dyes exhibit two-photon absorption in near infrared range.•SL4 displays 2PA activity when dissolved in water.•SL4 offers a potential application in two-photon fluorescence imaging.Designed to achieve high two-photon absorptivity dyes, a novel series of D-π-A type hydrosoluble inner salts (SL1, SL2, SL3 and SL4) based on pyridinium have been synthesized and fully characterized. Photophysical properties including linear absorption, one-photon excited fluorescence and two-photon absorption properties were systematically investigated. These results show that there is a shift in the absorption and emission maxima with variation of solvent polarity. Furthermore, the chromophore SL4 shows the strongest intensity of two-photon excited fluorescence among the four chromophores and the largest two-photon absorption cross-section in the near infrared region (∼960 nm), indicating the steric bulk of the electron-donating terminal group plays an important role in two-photon absorption behavior. In addition, SL4 displays two-photon absorption activity when dissolved in water, which can be effectively used in two-photon bioimaging for its reasonable two-photon absorption cross-section. SL4-labeled cells revealed a distinct vesicular localization, most likely representing lysosomal compartments.
Co-reporter:Zhaodi Liu, Ruilong Zhang, Qiong Zhang, Hongjuan Ding, Chuankui Wang, Shengli Li, Hongping Zhou, Shengyi Zhang, Jieying Wu and Yupeng Tian
RSC Advances 2014 vol. 4(Issue 6) pp:2620-2623
Publication Date(Web):04 Nov 2013
DOI:10.1039/C3RA43126F
The crystal structures and two-photon absorbing properties of trans-/cis-oligo(phenylene vinylene) derivatives were reported for the first time. Both experimental and theoretical results revealed that the two-photon absorption cross sections of them largely depend on their conformations.
Co-reporter:Yanqiu Liu, Hui Wang, Jun Zhang, Shengli Li, Chuankui Wang, Hongjuan Ding, Jieying Wu, Yupeng Tian
Optical Materials 2014 Volume 36(Issue 3) pp:687-696
Publication Date(Web):January 2014
DOI:10.1016/j.optmat.2013.11.014
•Two novel Nickel(II) complexes were designed, synthesized and fully characterized.•The Ni(II) complexes have higher electron delocalization.•The Nickel(II) complexes exhibit large two-photon absorption in narrow near-infrared range.•The Nickel(II) complexes exhibit superior optical power limiting property.•It possesses large values of the real part of the cubic hyperpolarizability χ(3).Two novel Nickel(II) complexes (NiL21 and NiL22) with remarkable two-photon absorption (TPA) and optical power limiting (OPL) properties were synthesized and fully characterized. Single crystals were obtained and solved by X-ray diffraction analysis. Their photophysical properties had been further investigated both experimentally and theoretically. The third-order nonlinear optical (NLO) properties (TPA and OPL) were investigated by open/closed aperture Z-scan measurements using femtosecond pulse laser in the range from 680 to 1080 nm. The results revealed that the two Nickel(II) complexes exhibited strong two-photon absorption and superior optical power limiting properties, which are much better than that of the free ligands.Graphical abstractTwo novel Nickel(II) complexes (NiL21 and NiL22) with remarkable two-photon absorption (TPA) and optical power limiting (OPL) properties were synthesized and fully characterized. Single crystals were obtained and solved by X-ray diffraction analysis. Their photophysical properties had been further investigated both experimentally and theoretically. The third-order nonlinear optical (NLO) properties (TPA and OPL) were investigated by open/closed aperture Z-scan measurements using femtosecond pulse laser in the range from 680 to 1080 nm. The results revealed that the two Nickel(II) complexes exhibited strong two-photon absorption and superior optical power limiting properties, which are much better than that of the free ligands.
Co-reporter:Rui Li, Dandan Li, Wenwen Fei, Jingyun Tan, Shengli Li, Hongping Zhou, Shengyi Zhang, Jieying Wu, Yupeng Tian
Optical Materials 2014 Volume 36(Issue 8) pp:1281-1288
Publication Date(Web):June 2014
DOI:10.1016/j.optmat.2014.03.003
•The chromophore of L3 exhibits good solubility in common organic solvents.•The chromophores (L1–3) exhibit large two-photon absorption.•The largest cross-section (δ) of L3 up to 8899 GM in the near-IR range.•The δmax/MW of the chromophores are 2.12 GM/g (L2) and 8.64 GM/g (L3).A series of triphenylamine-based chromophores (L1–3) with donor-π-donor (D-π-D) model have been designed and synthesized via solid phase Wittig reaction. Their one/two-photon fluorescence and electrochemical properties have been investigated. The results show that L2 and L3 exhibited strong and wide-dispersed two-photon-excited fluorescence (TPEF) in different solvents. Chromophore L3 displays the strongest intensity two-photon absorption activity and large cross-sections (>3600 GM) in the range of 680–840 nm in THF, the largest δ up to 8899 GM in the near-IR range, and the measured maximum TPA cross-sections per molecular weight (δmax/MW) is 8.64 GM/g (L3) in THF. Significantly, it also exhibits good solubility in common organic solvents when the chromophore was modified by polyether units as peripheral groups.
Co-reporter:Lin Kong, Jia-Xiang Yang, Long-Jiu Cheng, Peng Wang, Hong-Ping Zhou, Jie-Ying Wu, Yu-Peng Tian, Bao-Kang Jin, Xu-Tang Tao
Journal of Molecular Structure 2014 Volume 1059() pp:144-149
Publication Date(Web):5 February 2014
DOI:10.1016/j.molstruc.2013.11.017
•Crystals of a triphenylamine derivative in micro- and macro- size were investigated.•Weak interactions between adjacent molecules were computational calculated through DFT method to study the orientation growth.•The calculation result was helpful to understand the relationship of molecular structure and crystal growth process.In this study, a typical intramolecular charge transfer (ICT) triphenylamine derivative, [4-(diphenylamino)phenyl]methylenepropanedinitrile (abbreviated as DPMP) was synthesized. Controllable one dimensional (1D) nanocrystals of DPMP have been obtained through reprecipitation method. The thermodynamic relationship of the molecular structure and growth process in nanometer scale of DPMP was investigated through density functional theory (DFT) calculation, which was performed on the weak interactions between adjacent molecules. The results showed that the assembling interactions along a axis were much stronger than that along b and c axis, which meant that 1D orientation growth along a axis would be the most stable state in thermodynamics, that is to say, DPMP molecules tended to form 1D orientation structure. The study is helpful to understand the relationship of molecular structure, weak interactions, orientation growth process and self-assembling morphology.Graphical abstractCrystals in micro- and macro- size of [4-(diphenylamino)phenyl]methylene-propanedinitrile were investigated. Weak interactions between adjacent molecules were computational calculated through time-dependent density functional theory to understand the relationship between molecular structure and crystal growth process.
Co-reporter:Hui Wang, Abul Monsur Showkot Hossain, Qiong Zhang, Jieying Wu, Yupeng Tian
Inorganica Chimica Acta 2014 Volume 414() pp:153-159
Publication Date(Web):1 April 2014
DOI:10.1016/j.ica.2014.02.004
•Two novel dinuclear Cu(I) and Ag(I) complexes were designed, synthesized.•The molecular geometry optimization is based on crystal data.•The complexes display significantly enhanced two-photon absorption.•The Ag(I) complex possesses a large χ(3) in near IR region.A novel thiosemicarbazide ligand L and its dinuclear complexes M2(dppm)2L(NO3)2 [where dppm = bis(diphenylphosphino)methane, M = Cu(I) (1), Ag(I) (2)] were designed, synthesized and characterized by 1H NMR spectroscopy, elemental analysis, IR, MALDI-TOF mass spectroscopy, and single crystal X-ray diffraction analysis. The third-order nonlinear optical (NLO) properties of the metal complexes were determined by the open/close aperture Z-scan technique. The results reveal that the complexes possess much larger third-order nonlinear susceptibility and two-photon absorption cross sections than that of its free ligand L in the near IR region, especially for complex 2. The photophysical properties of them were investigated and interpreted on the basis of theoretical calculations (TD-DFT).A novel thiosemicarbazide ligand L and its dinuclear complexes M2(dppm)2L(NO3)2 [where dppm = bis(diphenylphosphino)methane, M = Cu(I) (1), Ag(I) (2)] were designed, synthesized and characterized by single crystal X-ray diffraction analysis.
Co-reporter:Jian Su;Liu-Di Yao;Jun Zhang;Jie-Ying Wu
Acta Crystallographica Section C 2014 Volume 70( Issue 2) pp:194-197
Publication Date(Web):
DOI:10.1107/S2053229614000047
The title novel noncentrosymmetric metal–organic framework, [Zn2Cl4(C17H20N8)]n, was prepared solvothermally using the tetradentate tetrakis[(imidazol-1-yl)methyl]methane (tiym) linker in the presence of zinc nitrate under acidic conditions. The asymmetric unit contains one ZnII cation, two Cl− anions and a quarter of each of two symmetry-independent tiym ligands. Each ZnII cation is four-coordinated by two Cl− anions and two imidazole N atoms from two tiym ligands, forming a distorted tetrahedral coordination geometry. The tetrahedral tetradentate tiym linker has a quaternary C atom located on a crystallographic axis. With its four peripheral imidazole N atoms, the linkers are bridged by four [ZnCl2] subunits to generate a three-dimensional diamond topological framework, which is represented by the Schläfli symbol {66}. To the best of our knowledge, the title compound is the first example of a non-interpenetrating diamond net based on the tiym ligand.
Co-reporter:Hui Wang;Wen-Mo Liu;Jun Zhang;Jie-Ying Wu
Acta Crystallographica Section C 2014 Volume 70( Issue 2) pp:185-188
Publication Date(Web):
DOI:10.1107/S2053229614000758
The crystal structure of the tetranuclear organotin compound 1,1,3,3,5,5,7,7-octabutyl-7-((E)-2-cyano-3-{9-[2-(2-methoxyethoxy)ethyl]-9H-carbazol-3-yl}prop-2-enoyloxy)-4,8-dimethyl-2,4,6,8-tetroxa-1,3,5,7-tetrastannatricyclo[4.2.0.02,5]oct-3-yl (E)-2-cyano-3-{9-[2-(2-methoxyethoxy)ethyl]-9H-carbazol-3-yl}prop-2-enoate, [Sn4(C4H9)8(C21H19N2O4)2(CH3O)2(μ3-O)2], consists of a core of three fused Sn2O2 rings. The central ring consists of two Sn atoms each coordinated by two n-butyl chains, two μ3-bridging O atoms and one μ2-bridging methanolate O atom. The peripheral Sn2O2 rings consist of one of the central ring Sn atoms, and an Sn coordinated by one μ3-bridging O atom, one μ2-bridging methanolate O atom, two n-butyl chains and the carboxylate O atom of a (E)-2-cyano-3-{9-[2-(2-methoxyethoxy)ethyl]-9H-carbazol-3-yl}prop-2-enoate ligand (L). Despite an apparent centrosymmetric nature, the complex does not crystallize about an inversion centre. The structure packs with π–π interactions between carbazole moieties on adjacent molecules.
Co-reporter:Fuying Hao, Zhaodi Liu, Mingliang Zhang, Jie Liu, Shengyi Zhang, Jieying Wu, Hongping Zhou, YuPeng Tian
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014 Volume 118() pp:538-542
Publication Date(Web):24 January 2014
DOI:10.1016/j.saa.2013.09.051
•We have synthesized four D–π–D dyes with two-photon absorption.•Four dyes contain phenothiazines/carbazoles with styrene/biphenylethyne as bridge.•Photophysical properties of four dyes were investigated.•Donors have larger contribution to σ value than that of conjugated bridge.•Four dyes can be used as organic two-photon photopolymerization initiators.A specific series of dumbbell-shaped bis-carbazoles or bis-phenothiazines dyes (1, 2, 3 and 4) constructed with styrene or biphenylethyne as the π-bridge have been synthesized and characterized. Detailed spectral properties including linear absorption, one and two-photon fluorescence properties were investigated. The results show that extending conjugated chain and introducing donors have substantial effect on their photophysical properties. Among them, two-photon absorption cross sections (σ) of the four dyes in DMF determined by the Z-scan technique are successively increased from 1 to 4 with enhancing electron-donating ability and extending conjugated chain, but electron-donating ability has larger contribution to the σ values than extending conjugated chain based on the comparison of small molecules (D–π–D). Two-photon initiation polymerization (TPIP) microfabrication experiments have been carried out using compound 4 as an initiator under irradiation of 200 fs, 76 MHz femtosecond laser at 760 nm. The results confirm that the four dyes can be effectively used as organic two-photon photopolymerization initiators.Graphical abstractA new series of dumbbell-shaped bis-carbazoles and bis-phenothiazines chromophores (1, 2, 3 and 4) constructed with styrene or biphenylethyne as the π-bridge have been synthesized and characterized. Experimental results revealed that extending conjugated chain and introducing donors have substantial effect on their photophysical properties. Compared with extending conjugated chain, enhancing electron-donating ability play a major role in enlarging two-photon absorption cross-sections (σ). Moreover, those four chromophores can be used as effectively organic two-photon photopolymerization initiators.
Co-reporter:Lin Kong;Jia-xiang Yang;Qi-yu Chen;Qiong Zhang
Journal of Nanoparticle Research 2014 Volume 16( Issue 3) pp:
Publication Date(Web):2014 March
DOI:10.1007/s11051-014-2324-3
A flurophore–phenothiazine derivative {2-[(10-ethyl-10H-phenothiazin-3-yl)-methylene] malononitrile, abbreviated as L} is designed, synthesized, and characterized by single crystal X-ray diffraction analysis. Further, L is used to couple with Au NPs to construct L–Au nanohybrid. Upon the coupling effect between L and Au components, blue-shifted photoluminescence with an obvious increased FL lifetime has been achieved. Surface enhanced Raman scattering analysis reveals that L molecules couple with Au NPs through S atoms. The coupling “hot spot” and the energy match between the Femi level of Au NPs and the frontier molecular orbital energy of L are effective factors in distributing the photogenerated electrons at the interface to tune the optical property.
Co-reporter:Qiong Zhang, Junshan Luo, Lili Ye, Hui Wang, Bei Huang, Jun Zhang, Jieying Wu, Shengyi Zhang, Yupeng Tian
Journal of Molecular Structure 2014 1074() pp: 33-42
Publication Date(Web):
DOI:10.1016/j.molstruc.2014.04.058
Co-reporter:Xuesong Zhao, Yanxin Chen, Junshan Luo, Hui Wang, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014 Volume 123() pp:30-36
Publication Date(Web):5 April 2014
DOI:10.1016/j.saa.2013.12.067
•Synthesis and characterization of two novel 6′-phenyl-2,2′-bipyridine ligands (L1, L2) and their CdL1,2I2 complexes are presented.•Single crystal study indicated that Cd(II) ion is in a distorted tetrahedral structure.•Linear absorption and single-photon exited fluorescence properties have been investigated.•The results showed that the complex 2 has the longest fluorescence lifetime.•Linear absorption spectral features are studied by TD-DFT methods.Two novel 6′-phenyl-2,2′-bipyridine ligands (L1, L2) and their CdL1,2I2 complexes (1, 2) were synthesized and characterized by elemental analysis, 1H NMR, IR, MALDI-TOF spectroscopy, and single crystal X-ray diffraction analysis. The results reveal that the central cadmium(II) atom in the complexes was coordinated by two iodide ions and two nitrogen atoms from L1, L2, forming a distorted coordination geometry. The electronic absorption properties of them were investigated on the basis of theoretical calculations (TD-DFT).Two novel 6′-phenyl-2,2′-bipyridine ligands (L1, L2) and their CdL1,2I2 complexes (1, 2) were designed, synthesized. Spectral properties were studied based on both experimentally and theoretically.
Co-reporter:Dandan Li, Nanqi Shao, Xianshun Sun, Guocui Zhang, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014 Volume 133() pp:134-140
Publication Date(Web):10 December 2014
DOI:10.1016/j.saa.2014.05.038
•Hybrid Tb(III) complexes based on D-π-A type dyes have been synthesized.•The structural features of them were systematic studied.•Linear absorption and emission spectra have been systematically investigated.•The energy transfer takes place from the pyridinium (2′) cation to Tb(III).Hybrid complexes based on D-π-A type dyes p-aminostyryl-pyridinum and Terbium(III) complex anion (1, 2) have been synthesized by ionic exchange reaction. Meanwhile two different alkyl-substituted amino groups were used as electron donors in organic dyes cations. The synthesized complexes were characterized by element analysis. In addition, the structural features of them were systematic studied by single crystal X-ray diffraction analysis. Their linear properties have been systematically investigated by absorption spectra and fluorescence, the results show that the energy transfer takes place from the trans-4-[4′-(N,N-diethylamino)styryl]-N-methyl pyridinium (2′) cation to Tb(III). In addition, complex 2 exhibit a large two-photon absorption coefficient β: 0.044 cm/GW at 710 nm.Hybrid complexes based on D-π-A type dyes p-aminostyryl-pyridinum and Terbium(III) complex anion (1, 2) have been synthesized by ionic exchange reaction. Meanwhile two different alkyl-substituted amino groups were used as electron donors in organic dyes cations. Their linear properties have been systematically investigated by absorption spectra and fluorescence, the results show that the energy transfer takes place from the trans-4-[4′-(N,N-diethylamino)styryl]-N-methyl pyridinium (2′) cation to Tb(III). In addition, complex 2 exhibit a large two-photon absorption coefficient β: 0.044 cm/GW at 710 nm.
Co-reporter:Lin Kong, Jia-xiang Yang, Zhao-ming Xue, Hong-ping Zhou, Long-jiu Cheng, Qiong Zhang, Jie-ying Wu, Bao-kang Jin, Sheng-yi Zhang and Yu-peng Tian
Journal of Materials Chemistry A 2013 vol. 1(Issue 33) pp:5047-5057
Publication Date(Web):07 Jun 2013
DOI:10.1039/C3TC30515E
A D–π–A type phenothiazine derivative 4-((E)-2-(10-ethyl-10H-phenothiazin-3-yl)-vinyl)-benzaldehyde (abbreviated as L) was designed, synthesized and characterized by single crystal X-ray diffraction analysis. Dispersion-corrected theoretical calculation revealed that L molecules tend to grow along a 1-dimensional (1-D) orientation. Further, L was used to prepare nanohybrids consisting of silver nanoparticles (NPs) dispersed on L nanoribbons. L molecules coupled with Ag NPs through S atoms, which brought about a significant blue-shift of the fluorescence (FL) and an obvious increase of FL lifetime. Through fluorescence microscopy, the spectral change was used as a wavelength-based biodetection tool to study the possible mechanism for an enhanced inhibitory effect of L–Ag nanohybrids on both gram-negative bacterium Escherichia coli and gram-positive bacterium Staphylococcus aureus compared to either pure Ag NPs or pure L.
Co-reporter:Dandan Li, Daohui Yu, Qiong Zhang, Shengli Li, Hongping Zhou, Jieying Wu, Yupeng Tian
Dyes and Pigments 2013 Volume 97(Issue 2) pp:278-285
Publication Date(Web):May 2013
DOI:10.1016/j.dyepig.2013.01.001
A novel stilbazolium salt with flexible chains, trans- [4-[N,N-bis(2-(2-methoxyethoxy)ethyl)amino]styryl]-N-methylpyridinium tetraphenylborate, was designed, synthesized and fully characterized. Third-order nonlinear optical properties for the new stilbazolium salt have been explored. The results show that the novel dye possesses very large values of the real part of the cubic hyperpolarizability χ(3), up to 10−12 esu, and displays maximum two-photon absorption cross sections within the narrow wavelength range from 950 to 960 nm, while out of the range, it shows a large real part of χ(3), which was determined by two-photon induced fluorescence and open/closed aperture Z-scan measurements using femtosecond pulse laser in near-infrared range, respectively.Highlights► A novel stilbazolium salt was designed and confirmed by crystallography. ► The molecular geometry optimization for calculation results from the crystal data. ► The photophysical properties were systematically investigated. ► The dye exhibits large two-photon absorption in narrow near-infrared range. ► It possesses large values of the real part of the cubic hyperpolarizability χ(3).
Co-reporter:Chao Tang, Qiong Zhang, Dandan Li, Jun Zhang, Pengfei Shi, Shengli Li, Jieying Wu, Yupeng Tian
Dyes and Pigments 2013 Volume 99(Issue 1) pp:20-28
Publication Date(Web):October 2013
DOI:10.1016/j.dyepig.2013.04.016
•Two novel bent-shaped dyes were confirmed by crystallography.•The molecular geometry optimization for calculation is from crystal data.•The photophysical properties of them were systematically investigated.•The two dyes exhibit strong two-photon absorption in near-infrared range.•The potential applications in two-photon biological imaging were evaluated.Two novel bent-shaped D–π–A–π–D chromophore molecules, 2-pyrazolyl-4,6-bis (4-N,N-ethylaminostyryl)pyrimidine (Z1) and 2-imidazolyl-4,6 –bis- (4-N,N- ethylaminostyryl) pyrimidine (Z2), were synthesized and fully characterized. It was found that the both bent-shaped chromophore molecules crystallize in the orthorhombic system, space group of P212121. The photophysical properties and the connections between structure and properties of the chromophores were investigated both experimentally and theoretically. It was revealed that both absorption and single-photon excited fluorescence (SPEF) spectra show remarkable bathochromic shifts with increasing polarity of the solvents. The two chromophores have strong two-photon excited fluorescence and large two-photon absorption cross-sections in the near-infrared range. Additionally, two-photon microscopy (TPM) fluorescent imaging of BEL-7402 cells labeled with the Z1 and Z2 revealed their potential application as a biological fluorescent probe.
Co-reporter:Qiong Zhang, Lin Li, Man Zhang, Zhaodi Liu, Jieying Wu, Hongping Zhou, Jiaxiang Yang, Shengyi Zhang and Yupeng Tian
Dalton Transactions 2013 vol. 42(Issue 24) pp:8848-8853
Publication Date(Web):08 Apr 2013
DOI:10.1039/C3DT50582K
Biological metal detecting, small molecule probes bearing nonlinear optical (NLO) response provide powerful alternatives due to their favorable photophysical properties (e.g. excitation wavelength in the near-IR region), cell permeability (due to their size), and chemical structure flexibility. Here, we present a series of pyrimidine-based NLO biological metal probes, especially a novel copper specific one which taken into account of the small volume-scaled and low cost-scaled nonlinear optical response of TPP and TPP–Cu2+ discussed in our present work. The photophysical properties of the probes were thoroughly investigated. 1H NMR and theoretical computation prove the binding interaction between the probe and the copper ion, which supports the functions of the molecule as a fluorescence signaling unit showing strong fluorescence quenching upon copper metal ion binding. On the other hand, the two-photon absorption cross-section of the novel copper probe increased from 275 to 591 GM (λex = 830 nm) after interacting with copper ion. It was further demonstrated that the NLO response for the copper(II) ion probe could be used for biological copper detection in live cells.
Co-reporter:Wen-wen Fei, Gui-ju Hu, Rui Li, Long-mei Yang, Sheng-li Li, Lei Tian, Jia-xiang Yang, Jie-ying Wu, Yu-peng Tian
Materials Chemistry and Physics 2013 Volume 139(2–3) pp:403-409
Publication Date(Web):15 May 2013
DOI:10.1016/j.matchemphys.2012.12.031
A series of novel metal complexes, ZnL2I2, CdL2I2, and HgL2I2 (L: 1-[Trans-4-(4-diethylaminostyryl) phenyl] imidazole), have been prepared and fully characterized. The structure of HgL2I2 was confirmed by single crystal X-ray diffraction analysis, which exhibits that Hg atom is coordinated by two iodine atoms and two nitrogen atoms from the ligand to form a distorted tetrahedral environment. The variable temperature 1H NMR spectra proved that the metal complexes exhibit well stability in solution. Linear and nonlinear optical properties of them were described on the basis of density functional theory (DFT) calculations. Interestingly, we found that the complexation of the ligands with metal ion extends the electronic delocalization in the metal complexes, leading to dramatically enhanced two-photon absorption.Highlights► Three d10-metal complexes with two-photon absorption (TPA) are reported. ► The crystal structure of HgL2I2 was determined. ► The complexes exhibit dramatically enhanced TPA related to its ligand. ► The connections between structure and properties for them were investigated.
Co-reporter:Shengli Li, Weibiao Shen, Guiju Hu, Qiong Zhang, Bing Liu, Jie Liu, Hongjuan Ding, Jieying Wu, Hongping Zhou, Jiaxiang Yang, Yupeng Tian
Materials Chemistry and Physics 2013 Volume 140(Issue 1) pp:200-207
Publication Date(Web):15 June 2013
DOI:10.1016/j.matchemphys.2013.02.073
•A novel chromophore with A′−D−A configuration was reported.•The structure was determined by single crystal X-ray diffraction analysis.•The relationships between the structures and properties were investigated.•The two-photon absorption cross-sections were determined by Z-scan technique.•The results indicate that auxiliary moiety (A′) largely influence on its properties.A novel chromophore (Z)-ethyl-3-(4-((4-([2,2′:6′,2″-terpyridin]-4′-yl)phenyl) (phenyl) amino)phenyl)-2-cyanoacrylate(3), constructed with triphenylamine moiety as the electron donor (D), 2, 2: 6, 2-terpyridine moiety as an electron acceptor (A), and ethyl cyanocaetate group as an auxiliary electron acceptor (A′), has been designed and synthesized. The crystal structures of 3 and its mediator 2 (4″-(4′-(4-(Diphenylamino) phenyl) aldehyde)-2,2′:6′,2″-Terpyridine), have been determined by single crystal X-ray diffraction analysis. The linear and nonlinear spectra of these chromophores were investigated on the basis of experimental and calculation methods. The two-photon absorption (TPA) cross-sections of 1–3 were determined by a femtosecond open-aperture Z-scan technique. The maximum value of the TPA cross-section (σ) for 3 is 7938.3 GM in DMF solution. However, much weaker two-photon absorption responses were observed at the same condition for chromophore 1 and 2, respectively. The results of the work indicate that, the photophysical properties of the D–A configuration group are influenced largely by the auxiliary moiety (A′) attached.
Co-reporter:Lin Kong;JiaXiang Yang;HongPing Zhou;ShengLi Li;FuYing Hao
Science China Chemistry 2013 Volume 56( Issue 1) pp:106-116
Publication Date(Web):2013 January
DOI:10.1007/s11426-012-4794-4
In this study, linear absorption, single-photon excited fluorescence, fluorescence quantum yields, fluorescence lifetime and two-photon excited fluorescence of a series of triphenylamine derivatives (L1, L2, L3 and L4) have been measured. L1 and L3 are D-π-A type dyes, while L2 and L4 are D-π-D-π-A type dyes (D = donor, A = acceptor). The investigated compounds consist of triphenylamine-bearing donor-substituted and/or systematically extended π-conjugated length, which are designed to gain insight into the effect of the ethoxyl unit and π-linkage length on the linear and nonlinear optical properties. The influence of solvent polarity on the photophysical properties was investigated. Employing time-dependent density functional theory (TD-DFT) calculations, the structure-property relationships are discussed.
Co-reporter: Lin Kong; Jia-xiang Yang; Sheng-li Li;Dr. Qiong Zhang; Zhao-ming Xue; Hong-ping Zhou; Jie-ying Wu; Bao-kang Jin; Yu-peng Tian
Chemistry - A European Journal 2013 Volume 19( Issue 49) pp:16625-16633
Publication Date(Web):
DOI:10.1002/chem.201302874
Abstract
A fluorophore–phenylamine derivative (L) has been coupled with silver nanocrystals (NCs) to construct an L–Ag nanohybrid. Owing to synergic effects of the L and Ag components, the exciton–plasmon interactions between L and Ag increase the strength of the donor–acceptor interaction within the nanohybrid, a fact that results in an energy-transfer process and further brings about a dramatic redshift of single-photon absorption and fluorescence, and a decreased fluorescence FL lifetime. The coupling effect also leads to enhancement of a series of nonlinear optical properties, including two-photon-excited fluorescence (TPEF), two-photon-absorption (TPA) cross section (δ), two-photon-absorption coefficient (β), nonlinear refractive index (γ), and third order nonlinear optical susceptibility (χ(3)). The enhanced two-photon fluorescence of the nanohybrid is proven to be potentially useful for two-photon microscopy of live cells, such as HepG2. Moreover, cytotoxicity tests show that the low-micromolar concentrations of the nanohybrid do not cause significant reduction in cell viability over a period of at least 24 h and should be safe for further biological studies.
Co-reporter:Xuchun Wang, Xiaohe Tian, Qiong Zhang, Pingping Sun, Jieying Wu, Hongping Zhou, Baokang Jin, Jiaxiang Yang, Shengyi Zhang, Chuankui Wang, Xutang Tao, Minhua Jiang, and Yupeng Tian
Chemistry of Materials 2012 Volume 24(Issue 5) pp:954
Publication Date(Web):December 13, 2011
DOI:10.1021/cm2029855
A novel cuprous(I) cluster Cu4I4L4 (L = (E)-(4-diethylanilino-styryl)pyridine) bearing strong two-photon absorption (TPA) was obtained using a facile assembly method, and the crystal structure has been determined. Quantum chemical calculations using time-dependent density functional theory (TD-DFT) reveals that the combination of the organic ligands with the three-dimensional Cu4I4 core extends the electronic delocalization in the cluster, leading to strong two-photon absorption action. The TPA cross sections (Φσ2) of Cu4I4L4 were enhanced with increasing polarity of solvents, which is quite different from the solvent effects on TPA in the literature. Compared to its free ligand, the cluster Cu4I4L4 exhibits larger peak TPA cross sections in the near-infrared region, longer fluorescence lifetimes, higher quantum yield and photostability, lower cytotoxicity, and brighter two-photon fluorescent (TPF) bioimaging. These integrated advantages make it desirable to be applied as a two-photon fluorescent probe for labeling the nucleic acids in live cells.Keywords: assembly; bioimaging; cuprous cluster; two-photon absorption;
Co-reporter:Shuangsheng Zhou, Qiong Zhang, Xiaohe Tian, Guiju Hu, Fuying Hao, Jieying Wu, Yupeng Tian
Dyes and Pigments 2012 Volume 92(Issue 1) pp:689-695
Publication Date(Web):January 2012
DOI:10.1016/j.dyepig.2011.06.021
An organic chromophore (4-[N, N- bis(2′-chloroethyl)anilino] ethenyl N-methyl pyridinium-N- methyl iodide) L was synthesized and fully characterized by elemental analysis, IR, 1HNMR spectra and single crystal X-ray diffraction analysis. One and two-photon fluorescence spectra for it were studied. Interestingly, L exhibited obvious two-photon absorption in the range from 700–850 nm in DMSO solution. The interactions between the chromophore and calf thymus DNA were investigated by absorption, fluorescence spectra and viscosity experiments. The results showed that the chromophore could interact with DNA in the mode of intercalation and be effectively used as fluorescent staining dye for cell imaging applications. Furthermore, the cell viability data for MCF-7 (Human breast carcinoma) cells indicated that the low-micromolar concentrations of the L are essentially non-toxic and can be applied in brighter two-photon fluorescent (TPF) bioimaging.An organic chromophore was synthesized and fully characterized by elemental analyses, IR, 1HNMR spectra and single crystal X-ray diffraction analysis. one and two-photon absorption properties, DNA-binding, and cell imaging of the new chromophore were investigated systematically. Interestingly, the chromophore exhibits obvious two-photon absorption in the range from 700–850 nm in DMSO solution, and be effectively used as fluorescent probes for cell imaging applications.Highlights► An organic chromophore was synthesized and fully characterized. ► The interactions between the chromophore and ctDNA in the mode of intercalation. ► The chromophore exhibits obvious two-photon absorption in NIR region in DMSO solution. ► The chromophore can be used as fluorescent staining dye for cell imaging applications.
Co-reporter:Qiong Zhang, Yuanhao Gao, Shengyi Zhang, Jieying Wu, Hongping Zhou, Jiaxiang Yang, Xutang Tao and Yupeng Tian
Dalton Transactions 2012 vol. 41(Issue 23) pp:7067-7072
Publication Date(Web):05 Apr 2012
DOI:10.1039/C2DT30622K
A novel sulfur-terminal Cd(II) complex, CdS2L (L = N-hexyl-3-{2-[4-(2,2′:6′,2′′-terpyridin-4′-yl)phenyl]ethenyl}-carbazole), was successfully synthesized from CdS nanocrystals and the organic chromophores (L), which was confirmed by single-crystal X-ray diffraction analysis. Its photophysical properties have been investigated both experimentally and theoretically. The novel hybrid nanoparticles (CdS/L) were then obtained using the L as surface capped agent, which aggregate into large spheres, exhibiting novel luminescent properties, strong two photon absorption (TPA) and obvious prolonged fluorescence lifetime, which differ from those of the pure CdS nanocrystals and free L.
Co-reporter:Wen-Qian Geng, Hong-Ping Zhou, Long-Huai Cheng, Fu-Ying Hao, Guo-Yi Xu, Fei-Xia Zhou, Zhi-Peng Yu, Zheng Zheng, Jian-Qing Wang, Jie-Ying Wu, Yu-Peng Tian
Polyhedron 2012 31(1) pp: 738-747
Publication Date(Web):
DOI:10.1016/j.poly.2011.10.032
Co-reporter:Y. K. Liang;B. F. Ruan;Y. P. Tian
Russian Journal of Coordination Chemistry 2012 Volume 38( Issue 6) pp:396-401
Publication Date(Web):2012 June
DOI:10.1134/S1070328412060097
9-Hexyl-9H-carbazole-3-carboxylic acid (LCOOH) and its complex with Ph3Sn(OH), [Ph3SnO2CL] (I), were synthesized. The structure of complex I was solved by single-crystal X-ray diffraction determination, indicating that I shows the discrete framework. Furthermore, this complex was tested in vitro for its cytotoxic activity, using human hepatocellular carcinoma cell line (BEL-7402) and human hepatocellular liver carcinoma cell line (HepG2); 5-fluorouracil was used as a positive control substance. This complex showed cytotoxicity greater than that of 5-fluorouracil.
Co-reporter:Zhang-Jun Hu, Xiao-He Tian, Xiang-Hua Zhao, Peng Wang, Qiong Zhang, Ping-Ping Sun, Jie-Ying Wu, Jia-Xiang Yang and Yu-Peng Tian
Chemical Communications 2011 vol. 47(Issue 46) pp:12467-12469
Publication Date(Web):28 Oct 2011
DOI:10.1039/C1CC14968G
A novel europium(III) β-diketonate complex exhibiting bright two-photon-sensitized luminescence is synthesized and applied as a two-photon-sensitized luminescent probe to stain DNA in live cells.
Co-reporter:Dongmei Li, Xiaohe Tian, Guiju Hu, Qiong Zhang, Peng Wang, Pingping Sun, Hongping Zhou, Xiangming Meng, Jiaxiang Yang, Jieying Wu, Baokang Jin, Shengyi Zhang, Xutang Tao, and Yupeng Tian
Inorganic Chemistry 2011 Volume 50(Issue 17) pp:7997-8006
Publication Date(Web):August 9, 2011
DOI:10.1021/ic200150h
Two bis-β-diketones, RCOCH2CO-EPTZ-COCH2COR (EPTZ = 10-ethylphenothiazine; R = C6H5 for H2L1 and CF3 for H2L2) and their cyclic dinuclear Zn(II), Cd(II), Ni(II), Mn(II), Cu(II), Co(II) complexes have been synthesized and fully characterized. Their crystal structures were determined by single crystal X-ray diffraction analysis. Their photophysical properties have been further investigated both experimentally and theoretically. The results revealed that significant enhancement of two-photon absorption cross section values were obtained for the cyclic dinuclear Zn(II) and Cd(II) complexes compared with their free ligands. Additionally, confocal microscopy and two-photon microscopy fluorescent imaging of MCF-7 cells labeled with two ligands and Zn(II) complexes reveal their potential applications as a biological fluorescent probe.
Co-reporter:Guiju Hu, Liangfei Lv, Lin Li, Qiong Zhang, Xianlei Li, Yupeng Tian, Jieying Wu, Baokang Jin, Hongping Zhou, Jiaxiang Yang, Shengyi Zhang
Dyes and Pigments 2011 Volume 89(Issue 2) pp:105-110
Publication Date(Web):May 2011
DOI:10.1016/j.dyepig.2010.09.011
A new D-A (Donor-Accept) type N-(1,2,4-triazolyl)-N′-(2-ethylhexyl) naphthalenediimide (L) was synthesized. AgL2PF6 (1) and AgL2NO3 (2) were obtained through the reactions of L with AgPF6 and AgNO3, respectively. All the compounds were fully characterized. Optical, electrochemical properties and electrogenerated chemiluminescence (ECL) were systematically investigated. Those dual fluorescent emissions for L, short wavelength (SW) and long wavelength (LW) emission bands, are rationally explained by the planar intramolecular charge transfer (PICT) model. All the compounds display anodically shift reduction waves with positive reduction potential, compared to its parent compound, Naphthalene bisimide (NBI). It is very interesting that the ECL intensity of the complexes is successfully increased, which is 20 times larger than that of L, explaining that the radical anions of the complexes are stabilized by coordinating L with Ag(I) ion. The results provide a new approach to study ECL materials.
Co-reporter:Banfeng Ruan, Yupeng Tian, Hongping Zhou, Jieying Wu, Rentao Hu, Chenhao Zhu, Jiaxiang Yang, Hailiang Zhu
Inorganica Chimica Acta 2011 Volume 365(Issue 1) pp:302-308
Publication Date(Web):15 January 2011
DOI:10.1016/j.ica.2010.09.024
Three novel organotin(IV) complexes with 2-(9H-carbazol-9-yl) acetic acid (HL), of the formulae {[nBu2SnOL]2O}2 (1), [nBuSn(O)OL]6 (2) and [nBu3SnOL]6 (3) were prepared. All compounds were characterized by X-ray crystallography, confirming that complex (1) is tetranuclear one with ladder framework, complex (2) is a hexanuclear organotin(IV) complex with drum structure and complex (3) is a macrocycle with 24-membered stannoxane ring. Furthermore, all complexes were tested in vitro for their cytotoxic activity, using human hepatocellular carcinoma cell line (BEL-7402) and human hepatocellular liver carcinoma cell line (HepG2). Complex (1) displayed the best cytotoxicity and can be pointed out as a promising substrate to be subject of further investigations.The antitumor activity of three novel organotin(IV) complexes had been studied against BEL-7402 and HepG2 tumor cell lines, observing that complex (1) showed powerful antitumor activity in vitro.
Co-reporter:Banfeng Ruan, Yupeng Tian, Rentao Hu, Hongping Zhou, Jieying Wu, Jiaxiang Yang, Hailiang Zhu
Inorganica Chimica Acta 2011 Volume 365(Issue 1) pp:473-479
Publication Date(Web):15 January 2011
DOI:10.1016/j.ica.2010.09.004
Two triorganotin(IV) carboxylates [nBu3SnOL]n (KK1) and [Ph3SnOL]n (KK2) have been prepared by the reactions of (E)-3-(4-(diphenylamino)phenyl)acrylic acid (HL) with n(Bu3Sn)2O and Ph3Sn(OH), respectively. Complexes KK1 and KK2 have been structurally characterized by IR, elemental analysis and X-ray crystallography, confirming that both complexes possess infinite 1D chain structures. It’s exciting to discover that KK1 and KK2 exhibit strong solid-state luminescence emission while the HL almost quenches. Furthermore, both complexes were assayed for in vitro antibacterial activity against two Gram-positive bacterial strains (Bacillus subtilis ATCC 6633 and Staphylococcus aureus ATCC 6538) and two Gram-negative bacterial strains (Pseudomonas aeruginosa ATCC 13525 and Escherichia coli ATCC 35218) by MTT method. Complex KK2 exhibited powerful antibacterial activities against S. aureus with MIC value of 0.78 μg/mL, which was superior to the positive controls penicillin G. On the basis of the biological results, structure–activity relationships were discussed.Two novel organotin(IV) complexes (KK1 and KK2) with 1D infinite chain structures had been studied against two Gram-positive bacterial strains (Bacillus subtilis ATCC 6633 and Staphylococcus aureus ATCC 6538) and two Gram-negative bacterial strains (Pseudomonas aeruginosa ATCC 13525 and Escherichia coli ATCC 35218) by MTT method in vitro.
Co-reporter:DongMei Li;Qiong Zhang;A. M. Showkot Hossain;Mei Sun
Science China Chemistry 2011 Volume 54( Issue 5) pp:730-736
Publication Date(Web):2011 May
DOI:10.1007/s11426-010-4141-6
Three bis-vinylpyridine compounds (4,4′-bis(2-vinylpyridine)biphenyl L1, 4,4′-bis(3-vinylpyridine) biphenyl L2, and 4,4′-bis (4-vinylpyridine)biphenyl L3) were synthesized by one-step solid-state reactions at room temperature, giving nearly quantitative yields. The compounds obtained were fully characterized by IR, MS and NMR spectroscopies. The structures of L2 and L3 were determined by single crystal X-ray diffraction analysis. No noticeable solvatochromism was observed in either one-photon absorption or one-photon excited fluorescence spectra. All of the compounds have high fluorescence quantum yields and long fluorescence lifetime. The linear and nonlinear optical properties of the compounds were investigated both experimentally and theoretically. Interestingly, the position of the nitrogen atom from pyridine influences their two-photon absorption across-sections.
Co-reporter:Mei-Lan Sun, Ban-Feng Ruan, Qiong Zhang, Zhao-Di Liu, Sheng-Li Li, Jie-Ying Wu, Bao-Kang Jin, Jia-Xiang Yang, Sheng-Yi Zhang, Yu-Peng Tian
Journal of Organometallic Chemistry 2011 696(20) pp: 3180-3185
Publication Date(Web):
DOI:10.1016/j.jorganchem.2011.06.045
Co-reporter:Zhao-Di Liu, Xuan-Jun Zhang, Jie-Ying Wu, Fu-Ying Hao, Hong-Ping Zhou, Yu-Peng Tian
Polyhedron 2011 30(2) pp: 279-283
Publication Date(Web):
DOI:10.1016/j.poly.2010.10.022
Co-reporter:Lin Kong, Jiaxiang Yang, Xiaopeng Hao, Hongping Zhou, Jieying Wu, Fuying Hao, Lin Li, Shengyi Zhang, Baokang Jin, Xutang Tao, Minhua Jiang and Yupeng Tian
Journal of Materials Chemistry A 2010 vol. 20(Issue 35) pp:7372-7377
Publication Date(Web):27 Jul 2010
DOI:10.1039/C0JM00004C
A carbazole derivative (3-(2,2-dicyanovinyl)-9-hexylcarbazole, abbreviated as L) has been designed, synthesized and used to prepare a novel organic–inorganic nanohybrid consisting of silver nanocrystals (Ag NCs) uniformly dispersed on the surface of L nanoribbons. Detailed characterizations have been performed. The results reveal that L couples with Ag NCs through a π-conjugated unit, which results in a significant red-shift of the fluorescence (FL), an obvious increase of FL lifetime and enhanced Raman scattering.
Co-reporter:Lin Li, Yupeng Tian, Jiaxiang Yang, Pingping Sun, Lin Kong, Jieying Wu, Hongping Zhou, Shengyi Zhang, Baokang Jin, Xutang Tao and Minhua Jiang
Chemical Communications 2010 vol. 46(Issue 10) pp:1673-1675
Publication Date(Web):11 Jan 2010
DOI:10.1039/B918841J
The accurate photophysical data of dye-concentrated nanoparticles have been measured by the strategy of constructing ethoxysilane hydrolysis-assisted nanomaterials, which give rise to a large enhancement in two-photon absorption.
Co-reporter:Fuying Hao, Xuanjun Zhang, Yupeng Tian, Hongping Zhou, Lin Li, Jieying Wu, Shengyi Zhang, Jiaxiang Yang, Baokang Jin, Xutang Tao, Guangyong Zhou and Minhua Jiang
Journal of Materials Chemistry A 2009 vol. 19(Issue 48) pp:9163-9169
Publication Date(Web):23 Oct 2009
DOI:10.1039/B914656C
A new series of hybrid dyes, trans-4-(4′-N,N-dialkylaminostyryl)-N-methyl pyridinium [Cd(SCN)3−]n [alkyl = Me(1), Et(2), Pr(3) and n–Bu(4)] have been successfully synthesized from hybrids of inorganic polymers and organic chromophores. The structures of four new hybrid dyes were characterized by single-crystal X-ray diffraction first. The particular features of the hybrid dyes are (1) the inorganic anions form isolated polymeric one-dimensional zig-zag chains of [Cd(SCN)3−]n with an extended π-conjugation system within the polymeric –[M–S–C≡N]–M… chain and high polarizabilities; and (2) the organic cationic chromophores determine their optical properties. Experimental results revealed that the TPA cross-section values and overall energy conversion efficiencies of hybrid dyes with different alkyl pendant groups have obviously increased from 1 to 4, and in particular, have been substantially enhanced compared to their corresponding iodide analogues 1′–4′. Therefore, we speculate that such increases are attributable to arrangements of infinite anionic [Cd(SCN)3−]n chains and synergic effects with chromophore cations.
Co-reporter:Yuan-Hao Gao, Wen Zhou, Lin Li, Jie-Ying Wu, Hong-Ping Zhou, Jia-Xiang Yang and Yu-Peng Tian
Crystal Growth & Design 2009 Volume 9(Issue 1) pp:253
Publication Date(Web):November 21, 2008
DOI:10.1021/cg8004085
4′-(4-{2-[4-(N,N-diphenylamino)phenyl]ethenyl}phenyl)-2,2′:6′,2′′-terpyridine is a highly conjugated compound, which is used to grow polymorphs. The results obtained suggest that polymorphs could appear as the Eu3+/Ag+-induced feature. Only three intermolecular C−H···π interactions stabilize the polymorph A in monoclinic space group C2/c with Z = 8, while five intermolecular C−H···π interactions assume completely new pattern to arrange the Eu3+/Ag+-induced polymorph B in monoclinic space group P21/c with Z = 4. The changes in patterns of the C−H···π interactions could impose on the molecular conformation, induced dipole, electronic delocalization and intra- and intermolecular electron transfer transition, and thus give rise to the very different photoelectric response for polymorphic forms.
Co-reporter:Dongmei Li, Liangfei Lv, Pingping Sun, Wen Zhou, Peng Wang, Jieying Wu, Yuhe Kan, Hongping Zhou, Yupeng Tian
Dyes and Pigments 2009 Volume 83(Issue 2) pp:180-186
Publication Date(Web):November 2009
DOI:10.1016/j.dyepig.2009.04.006
Two blue emitters, 3,7-bis(5′-(trifluoromethyl)-1′H-pyrazole-3′-yl)10-ethylphenothiazine and 3,7-bis(5′-(phenyl)-1′H-pyrazole-3′-yl)10-ethyl-phenothiazine and one red, bis-dioxaborine emitter, each based on two, yellow-green emitting, bis-β-diketonate, phenothiazine derivatives, were obtained in high yield and characterized. Systematic investigation of the two-photon absorption characteristics was carried out using one-photon absorption, one-photon excited fluorescence as well as two-photon excited fluorescence spectra. TDDFT computational studies were undertaken to secure an insight into the nature of the compounds' electrochemical and photophysical properties. Low-energy absorption transmissions resemble those observed for the experimental one-photon absorption spectra.
Co-reporter:Yu-Peng Tian, Lin Li, Yong-Hong Zhou, Peng Wang, Hong-Ping Zhou, Jie-Ying Wu, Zhang-Jun Hu, Jia-Xiang Yang, Lin Kong, Gui-Bao Xu, Xu-Tang Tao and Min-Hua Jiang
Crystal Growth & Design 2009 Volume 9(Issue 3) pp:1499
Publication Date(Web):January 22, 2009
DOI:10.1021/cg801022h
Two new donor−bridge−acceptor (D−π−A) type ligands (L1: trans-4-[(p-N,N-dimethylamino)styryl]-N-acetic-acid pyridinium and L2: trans-4-[(p-N-2-hydroxyethyl-N-methylamino)styryl]-N-acetic-acid pyridinium) were designed and synthesized, which have double functions, two-photon absorption and coordination ability. Fourteen novel rare earth complexes have been prepared by the reaction of rare earth salts with the two ligands in ethanol solution, respectively. The two novel ligands and their complexes were characterized by single crystal X-ray diffraction determination. Linear and nonlinear optical properties of the ligands and three representative complexes are described. All these compounds exhibit relatively large two-photon absorption (TPA) cross sections. When pumped by a 1064 nm laser beam, two-photon-pump cavity lasing was observed in these compounds. Analysis of the lasing efficiencies and TPA cross sections show that rare earth ions have a significant influence on two-photon absorption properties of the complexes by adjusting the density of the chromophores.
Co-reporter:Yuanhao Gao, Jieying Wu, Qiong Zhao, Lingxia Zheng, Hongping Zhou, Shengyi Zhang, Jiaxiang Yang and Yupeng Tian
New Journal of Chemistry 2009 vol. 33(Issue 3) pp:607-611
Publication Date(Web):14 Jan 2009
DOI:10.1039/B815115F
By using a novel terpyridine-based dye as a surface stabilizing agent, novel dye-capped Ag nanocrystals (NCs) were obtained. The growth dynamics of these dye-capped Ag NCs were monitored by UV-vis absorption spectroscopy. Interactions between the dye and the Ag NCs were investigated by 1H NMR spectroscopy. The dye-capped Ag NCs showed solvent-resolved fluorescence in organic solvents, with full width at half-maximums (FWHM) as wide as ∼100 nm, demonstrating the effect of the Ag NCs on the enhanced fluorescence of the capping dye.
Co-reporter:Dongmei Li;Rentao Hu;Wen Zhou;Pingping Sun;Yuhe Kan;Yupeng Tian;Hongping Zhou;Jieying Wu;Xutang Tao;Minhua Jiang
European Journal of Inorganic Chemistry 2009 Volume 2009( Issue 18) pp:2664-2672
Publication Date(Web):
DOI:10.1002/ejic.200900216
Abstract
(E)-3-(10-ethylphenothiazine-3-yl)acrylic acid (LCOOH) was synthesized. LCOOH reacted with Ph3Sn(OH) and nBu2SnO to afford Ph3SnO2CL (1) and {[nBu2SnO2CL]2O}2 (2), respectively. The structures of all the compounds were solved by single-crystal X-ray diffraction. Compounds 1 and 2 present discrete and ladder frameworks, respectively. The one-photon absorption and excited fluorescence, and two-photon excited fluorescence spectra of all the compounds were systematically investigated. The results show that the two organostannoxanes exhibit much more enhanced two-photon absorption properties than LCOOH. TDDFT computational studies have been performed to elucidate the electronic structures of the ground state of LCOOH.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Co-reporter:Yuanhao Gao, Qian Zhang, Qiang Gao, Yupeng Tian, Wen Zhou, Lingxia Zheng, Shengyi Zhang
Materials Chemistry and Physics 2009 Volume 115(2–3) pp:724-727
Publication Date(Web):15 June 2009
DOI:10.1016/j.matchemphys.2009.02.020
High quality CdSe quantum dots are synthesized through a solution-phase synthesis technique with Cd(CH3COO)2·2H2O and Na2SeSO3 as precursors. In this synthesis approach, the participation of a novel terpyridine derivative provides much better control over growth dynamics of CdSe quantum dots, resulting in the suppression of the Ostwald ripening process of the particle size distribution during growth. The CdSe quantum dots meet the all requirements of high quality quantum dots.
Co-reporter:Zhang-Jun Hu, Ping-Ping Sun, Lin Li, Yu-Peng Tian, Jia-Xiang Yang, Jie-Ying Wu, Hong-Ping Zhou, Li-Ming Tao, Chuan-Kui Wang, Ming Li, Guang-Hua Cheng, Huo-Hong Tang, Xu-Tang Tao, Min-Hua Jiang
Chemical Physics 2009 Volume 355(2–3) pp:91-98
Publication Date(Web):27 January 2009
DOI:10.1016/j.chemphys.2008.10.031
Abstract
Two novel asymmetric D–π–D′ type chromophores with blue two-photon-excited fluorescences, (E)-3-(4-(methylthio)styryl)-9-ethyl-carbazole (T1) and (E)-3-(4-(methylthio)styryl)-9-hexyl-carbazole (T2), were synthesized via a solvent-free Wittig–Horner reaction. All of the compounds obtained were fully characterized by IR, MS and NMR spectroscopies. The structure of T1 was determined by single crystal X-ray diffraction analysis. A mechanism for the formation of the target molecules is also presented. Linear and nonlinear optical properties of T1 and T2 were investigated both experimentally and theoretically. The results show that the two asymmetric D–π–D′ type dyes exhibit clear two-photon activities with efficient blue emissions. Finally, pilot studies based on nonlinear optical applications of the synthesized chromophores were also carried out.
Co-reporter:Banfeng Ruan, Yupeng Tian, Hongping Zhou, Jieying Wu, Zhaodi Liu, Chenhao Zhu, Jiaxiang Yang, Hailiang Zhu
Journal of Organometallic Chemistry 2009 694(18) pp: 2883-2887
Publication Date(Web):
DOI:10.1016/j.jorganchem.2009.04.020
Co-reporter:Lin Li Dr.;Jia-Xiang Yang Dr.;Ping-Ping Sun;Jie-Ying Wu ;Hong-Ping Zhou Dr.;Sheng-Yi Zhang Dr.;Bao-Kang Jin Dr.;Xiao-Juan Xing;Chuan-Kui Wang ;Ming Li;Guang-Hua Cheng ;Huo-Hong Tang;Wen-Hao Huang ;Xu-Tang Tao ;Min-Hua Jiang
Chemistry – An Asian Journal 2009 Volume 4( Issue 5) pp:668-680
Publication Date(Web):
DOI:10.1002/asia.200800402
Co-reporter:RenTao Hu;LiangFei Lü;BanFeng Ruan;Peng Wang
Science China Chemistry 2009 Volume 52( Issue 8) pp:1210-1215
Publication Date(Web):2009 August
DOI:10.1007/s11426-009-0039-6
Two carbazole-based polymerization initiators possessing blue fluorescence emission have been synthesized via Wittig reaction in the solid phase at room temperature. Two-photon excited fluorescence (TPEF) spectra for them were investigated under 800 nm fs laser pulse and two-photon absorption cross sections were determined by the Z-scan technique. Then two-photon initiating polymerization (TPIP) microfabrication experiments were successfully carried out. Three-dimensional lattice and artificial defects were gained, indicating that they were viable candidates for the two-photon polymerization initiator in practical application of microfabrication.
Co-reporter:LeHua Cheng;Lin Li;PingPing Sun;HongPing Zhou
Science China Chemistry 2009 Volume 52( Issue 4) pp:529-534
Publication Date(Web):2009 April
DOI:10.1007/s11426-009-0026-y
Two triphenylamine-based derivatives that can be used as two-photon absorption chromophore, tris{4-[4-(3-trifluoromethyl-3-oxopanoyl)]phenyl}amine (1) and tris{4-[4-(3-phenyl-3-oxopanoyl)] phenyl} amine (2) were successfully synthesized and fully characterized by elemental analysis, IR, 1H NMR and MS. The single crystal X-ray diffraction analysis showed that the molecules possess D-(π-A)3 structures. One-and two-photon absorption and fluorescence in various solvents were experimentally investigated. A data recording experiment proved the potential application of these chromophores.
Co-reporter:Mei Sun, Peng Wang, Hongping Zhou, Jiaxiang Yang, Jieying Wu, Yupeng Tian, Xutang Tao, Minhua Jiang
Journal of Molecular Structure 2008 Volume 873(1–3) pp:73-78
Publication Date(Web):17 February 2008
DOI:10.1016/j.molstruc.2007.03.019
Two novel 1D infinite chain coordination polymers, [CdL(NO3)2]n and [CoL(NO3)2]n (L = 4,4′-bis[2-(2-pyridyl)ethenyl]biphenyl) have been prepared by reacting Cd(NO3)2 and Co(NO3)2 with the novel ligand L. Complexes 1 and 2 have been characterized by elemental analysis, IR and single crystal X-ray diffraction determination. The metal ions in the polymers have six coordinate pseudo octahedral structures with two pyridyl nitrogen atoms of L and four oxygen atoms of nitrate. The ligand coordinates to metal ions forming bridges in different geometries (cis and trans coordination modes). The results of TGA determination show that the coordination polymers are quite thermally stable. The complexes exhibit a strong emission band with the maximum intensity at 524 and 545 nm in solid-state, respectively, upon excitation at 350−450 nm.
Co-reporter:Lin Yang;Xiang-Hua Zhao;Hong-Ping Zhou;Jie-Ying Wu
Transition Metal Chemistry 2008 Volume 33( Issue 4) pp:431-437
Publication Date(Web):2008 May
DOI:10.1007/s11243-008-9061-3
Two bis-(β-diketonate) ligands [H2L1 = 3,6-bis-(4,4,4-trifluorobutane-1,3-dione)-9-butyl-carbazole and H2L2 = 3,6-bis-(4,4,4-trifluorobutane-1,3-dione)-9-hexyl-carbazole] were synthesized, and their corresponding dinuclear ruthenium(II) complexes [Ru2(bpy)4(L1)](PF6)2 (1) and [Ru2(bpy)4(L2)](PF6)2 (2) (bpy = 2,2′-bipyridine)] were prepared by the reaction of Ru(bpy)2Cl2 · 2H2O with H2L1 and H2L2 in ethanol, respectively. The structure of the ligand H2L2 was determined by single-crystal X-ray diffraction. The spectral properties of the ligands and their complexes have been studied. The absorption spectra of the complexes exhibit intense ligand-centered bands in the UV region and metal-to-ligand charge-transfer bands in the visible region. The two-photon absorption (TPA) coefficient β and TPA cross-section σ were determined by the Z-scan technique, which revealed that the two complexes exhibit strong TPA due to electronic extensive delocalization. The complexes undergo a reversible or quasi-reversible one-electron metal-centered redox process at E1/2 = +0.93 V and E1/2 = +0.92 V, respectively.
Co-reporter:Yu-Peng Tian, Lin Li, Ju-Zhou Zhang, Jia-Xiang Yang, Hong-ping Zhou, Jie-ying Wu, Ping-ping Sun, Li-min Tao, Ya-hui Guo, Chuan-Kui Wang, Hui Xing, Wen-hao Huang, Xu-Tang Tao and Min-Hua Jiang
Journal of Materials Chemistry A 2007 vol. 17(Issue 34) pp:3646-3654
Publication Date(Web):02 Jul 2007
DOI:10.1039/B703853D
Six centrosymmetric D–(π–A)3 structural triphenylamine derivatives that can be used as two-photon photopolymerization and optical data storage chromophores, tris[4-(4-pyridylethenyl)phenyl]amine (1), tris[4-(2-pyridylethenyl)phenyl]amine (2), tris(4-cyanoethenylphenyl)amine (3), tris[4-butylacrylatephenyl]amine (4), tris[4-methylacrylatephenyl]amine (5) and tris[4-acrylicethenylphenyl]amine (6), have been successfully synthesized via a triple palladium-catalyzed Heck coupling reaction, and the novel chromophores were fully characterized by elemental analysis, IR, 1H-NMR and ESIMS. The structure for 3 was determined by single crystal X-ray diffraction study. One- and two-photon absorption and fluorescence in various solvents were experimentally investigated. Two-photon initiated polymerization microfabrication and optical data recording experiments were carried out under 780 nm laser radiation, and the possible polymerization mechanism is discussed based on theoretical calculations. All the six chromophores have relatively large two-photon absorption cross-sections, and exhibit optical memory and highly efficient two-photon initiated polymerization abilities.
Co-reporter:Lei Tian, Zhangjun Hu, Pengfei Shi, Hongping Zhou, Jieying Wu, Yupeng Tian, Yufang Zhou, Xutang Tao, Minghua Jiang
Journal of Luminescence 2007 Volume 127(Issue 2) pp:423-430
Publication Date(Web):December 2007
DOI:10.1016/j.jlumin.2007.02.040
The title compounds, several Schiff bases with D–π–D type have been successfully synthesized from reaction of 4-(N-dialkylamino) benzaldehyde and hydrazine or p-phenylenediamine in ethanol. These compounds were characterized by IR, 1H NMR, elemental analysis and electronspray mass spectrometry. One-photon fluorescence and two-photon fluorescence properties have been investigated. The two-photon absorption (TPA) cross section (σ) of these compounds was obtained by using the open-aperture Z-scan technique. Based on theoretical calculations and factual test, the influence that a series of substituted groups and the conjugated frame imposed on TPA cross section were systematically discussed.
Co-reporter:Hong-Ping Zhou;Peng Wang;Zhang-Jun Hu;Lin Li;Jing-Jin Chen;Yang Cui;Jie-Ying Wu;Jia-Xiang Yang;Xu-Tang Tao;Min-Hua Jiang
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 13) pp:
Publication Date(Web):20 MAR 2007
DOI:10.1002/ejic.200600887
Two functional, flexible ligands, namely 3,6-dipyrazolyl-9-ethylcarbazole (L1) and 3,6-diimidazolyl-9-ethylcarbazole (L2) have been synthesized and characterized and their coordination to various AgI, CdII, and CoII salts investigated. Six new complexes, 1–6, have been obtained and fully characterized by IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The 2D double helix framework of the complex [CdL1I2]n (1) is formed by C–H···I hydrogen bonds, whereas the same 2D double helix framework of compound [{AgL1SO3PhCH3}2(CH3OH)(H2O)]n (2) is formed by S–O···H and C–H···O hydrogen bonds and weak π–π interactions. The coordination modes of CdII and CoII in [CdL22(NCS)2]n (3), [CoL22(NCS)2(CHCl3)2]n (4), [CdL22(NO3)2(CH3OH)2]n (5), and [CoL22(NO3)2(CH3OH)2]n (6) are the same, but in the packing diagram interlayers form a 3D network through C–H···S interactions and π–π interactions in 3, interlayers form a 3D network through S···S interactions and π–π interactions in 4, novel 3D structures are formed by interchain O···H–C hydrogen bonding and interlayer O···H–C hydrogen-bonding and π–π interactions in 5 and 6. The structural differences between these complexes show the influence of the orientation of the coordinating group of the ligand. These results also show that the metal ion, anion, and nonbonding and π–π interactions are significant factors in controlling the structural topology of these metal-organic supramolecular architectures. In addition, the luminescence properties of L1, 1, L2, and 3 are investigated in the solid state at room temperature. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Yu-Peng Tian;Yong-Min Zhu;Hong-Ping Zhou;Peng Wang;Jie-Ying Wu;Xu-Tang Tao;Min-Hua Jiang
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 2) pp:
Publication Date(Web):9 NOV 2006
DOI:10.1002/ejic.200600712
Three novel functional transition-metal complexes with H2A (H2A = 9-ethylcarbazole-3,6-dicarboxylic acid), Cd(HA)2(H2O)2 (1), [Cd(A)(phen)]·1.5H2O (2) (phen = 1,10-phenanthroline), and Cd(HA)2(bipy) (3) (bipy = 4,4′-bipyridine), have been successfully synthesized by a hydrothermal synthetic method and characterized by single-crystal X-ray diffraction, infrared spectroscopy, elemental analysis, thermogravimetric analysis, and photoluminescence. The results show that all of the complexes contain nanometer channels, while the coordination modes were changed by the addition of the mixed ligands. The 2D supramolecular open-framework 1 is constructed through hydrogen-bond and aromatic π–π interactions. 2D coordination polymer 2 is constructed by π–π interactions between adjacent metal-organic polymeric coordination chains. Interestingly, the 3D supramolecular architecture of 3 first formed 2D grid layers from 1D chains by intermolecular hydrogen bonds and then extended into a 3D structure through aromatic π–π interactions. Furthermore, strong emissions from these complexes were also changed by the coordination modes in the solid state. However, complexes 1–3 show high thermal stability.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Zhang-Jun Hu, Jia-Xiang Yang, Yu-Peng Tian, Hong-Ping Zhou, Xu-Tang Tao, Gui-Bao Xu, Wen-Tao Yu, Xiao-Qiang Yu, Min-Hua Jiang
Journal of Molecular Structure 2007 Volume 839(1–3) pp:50-57
Publication Date(Web):27 August 2007
DOI:10.1016/j.molstruc.2006.10.044
Two donor-π-acceptor (D-π-A) type 2,2′: 6′,2″-terpyridyl-based organic heterocyclic molecules have been efficiently synthesized via solvent-free Wittig reactions in good yields. One crystal structure of them was determined by single crystal X-ray diffraction determination. The two compounds exhibit sensitive single-photon-excited fluorescence (SPEF) emission with high fluorescence quantum yields and long lifetimes. The two-photon-excited fluorescence (TPEF), two-photon absorption (TPA) cross-sections and two-photon initiation polymerization (TPIP) microfabrication experiments have been investigated. Experimental results confirm that they are effective organic two-photon photopolymerization initiators.
Co-reporter:Hong-ping Zhou, Dong-mei Li, Peng Wang, Le-hua Cheng, Yuan-hao Gao, Yong-min Zhu, Jie-ying Wu, Yu-peng Tian, Xu-tang Tao, Min-hua Jiang, Hoong-Kun Fun
Journal of Molecular Structure 2007 Volume 826(2–3) pp:205-210
Publication Date(Web):29 January 2007
DOI:10.1016/j.molstruc.2006.05.003
A new bidentate Schiff base ligand (abbreviated as L) derived from the condensation of S-methyldithiocarbazate (SMDTC) with 9-fluorenone, and its complexes ML2 (M = Ni(II), Zn(II) and Pd(II)) have been synthesized and fully characterized by elemental analyses, IR, molar conductivity and UV–vis spectroscopy. The structures of complexes ZnL2 and PdL2 have been determined by X-ray diffraction analysis. Complex ZnL2 adopts a distorted tetrahedral geometry with the azomethine nitrogen atom and the thiolate sulfur atom. The coordination geometry about the Pd(II) is surprisingly a cis-configuration square-planar formed by the Pd(II) atom coordinating to the NS bidentate ligand. Detailed crystal structure analyses show that the cis-positioning of the two ligands was stabilized by the π–π stacking interactions between the two delocalized diazafluorene moieties. The two-photon absorption of L and ML2 solutions (in DMF) was measured at 532 nm by the open-aperture Z-scan technique.
Co-reporter:Feng Jin, Jian-feng Li, Hong-ping Zhou, Jie-ying Wu, Jia-xiang Yang, Yu-peng Tian, Min-hua Jiang
Journal of Molecular Structure 2007 Volume 829(1–3) pp:202-207
Publication Date(Web):17 March 2007
DOI:10.1016/j.molstruc.2006.06.025
A novel imidazole derivative, 1-[trans-4-(4-diethylaminostyryl)phenyl]imidazole (abbreviated as L), and its complex Zn(SCN)2L2 have been synthesized and fully characterized. Their crystal structures have been determined by X-ray diffraction. The molecular structure of L is approximately coplanar, the bond lengths of C–C and C–N are located between the normal double and single bonds, which show that L has a delocalized π-electron system in the molecule. In the molecular structure of Zn(SCN)2L2, zinc atom is four coordinated by two nitrogen atoms of the ligands (L) and two nitrogen atoms of thiocyanate to form a distorted tetrahedral geometry. The one-dimensional structure of Zn(SCN)2L2 is formed by C–H⋯S interactions and π–π interactions. They both crystallize in the noncentrosymmetric space group P21, and exhibit powder second-harmonic generation (SHG) efficiency approximately twenty times high as that of urea, indicating promising potential applications as useful nonlinear optical (NLO) materials.
Co-reporter:Jie-Ying Wu, Yue-Li Pan, Xuan-Jun Zhang, Tao Sun, Yu-Peng Tian, Jia-Xiang Yang, Zhong-Ning Chen
Inorganica Chimica Acta 2007 Volume 360(Issue 6) pp:2083-2091
Publication Date(Web):20 April 2007
DOI:10.1016/j.ica.2006.10.043
A series of carbazole-functionalized carboxylate ligands (N-carbazolylacetic acid (L1), 4-carbazol-9-yl-benzoic acid (L2), and 3-(4-carbazol-9-yl-phenyl)-acrylic acid (L3)) and their corresponding silver complexes were designed and synthesized and the structures were determined by single crystal X-ray diffractions. The silver atoms in the complexes are in tetrahedral geometry coordinated with two oxygen from carboxylic and two phosphorous atoms from triphenylphosphine. The complexes exhibit excellent electrochemical characters in solution and strong photoluminescence in the solid state. The emission wavelengths of the compounds can be tuned (from ultraviolet to visible region) by introducing of the second coordinating ligand triphenylphosphine and by elongation of the conjugation moieties.A series of carbazole-functionalized carboxylate ligands and silver complexes were obtained. The emissions of their photoluminescence can be tuned by introducing of the second coordinating ligand and/or by elongation of the conjugation moieties.
Co-reporter:Tao Sun;Yue li Pan;Jie ying Wu;Hong ping Zhou;Zu zhi Zhao
Transition Metal Chemistry 2007 Volume 32( Issue 4) pp:449-455
Publication Date(Web):2007 May
DOI:10.1007/s11243-007-0186-6
New nonpolymeric diruthenium (II, III) carboxylates of the type [Ru2(μ-O2CR)4Cl] [R = 9-methyl-9H-carbazole, 9-phenyl-9H-carbazole, 9-(4-vinylphenyl)-9H-carbazole] were obtained by reaction of HO2CR with [Ru2(μ-O2CCH3)4Cl] in MeOH–H2O. All complexes were characterized by TG, electron spectroscopy, cyclic voltammetry, and ESR spectra. The solvent influence on fluorescence was also discussed. Simultaneously, the electrochemical properties of these complexes were discussed in terms of the most probable electronic configuration of the complexes in solution. The frozen-solution e.s.r. spectra at 110 K give g = 1.94, 1.99, 1.95 for Ru2(L0)4Cl, Ru2(L1)4Cl and Ru2(L2)4Cl, respectively. The complexes in DMF solution exhibited strong two-photon absorption (t.p.a.) at 532 nm nanosecond laser pulse. Their t.p.a. coefficient β, t.p.a. cross-section δ have been determined by the Z-scan technique.
Co-reporter:Yong-Min Zhu;Wei-Jie Li;Liang-Fei Lv;Peng Wang
Transition Metal Chemistry 2007 Volume 32( Issue 7) pp:967-970
Publication Date(Web):2007 October
DOI:10.1007/s11243-007-0267-6
A novel two-dimensional supramolecular complex, Mn(HA)2(H2O)2 (1) (H2A: 9-ethylcarbazole-3,6-dicarboxylic acid) has been prepared by hydrothermal synthetic method and characterized by X-ray single crystal diffraction, IR spectra, elemental analysis and TG analysis. The result confirms that complex (1) crystallizes in the space group C2/c with a = 31.30(2) Å, b = 5.088(4) Å, c = 20.517(14) Å, β = 119.863(9)°, Z = 4, V = 2834(3)Å3. The 2D supramolecular open framework (1), which contains 9.773 × 7.447 Å nanometer channels, is constructed through hydrogen bonds and aromatic π − π interactions. Furthermore, the solid-state fluorescent analyses show that complex 1 exhibits a broad emission with the maximal emission at 416 nm.
Co-reporter:Xu-Chun Wang;Jian-Feng Li;He-Ping Chen;Jie-Ying Wu
Transition Metal Chemistry 2007 Volume 32( Issue 5) pp:551-557
Publication Date(Web):2007 August
DOI:10.1007/s11243-007-0200-z
The novel compound, 3-(E)-ferrocenyl-vinyl-N-hexylcarbazole (FVHC) was first synthesized and fully characterized by elemental analysis, IR, 1H-NMR, single-crystal X-ray diffraction, ultraviolet (UV) absorption, cyclic voltammograms (CV) and optical limiting (OL) measurements. The result of single crystal X-ray diffraction for the compound reveals that the ferrocenyl and carbazole groups are approximately coplanar, and bridged by double-bond with E configuration, showing that there is a well-delocalized π-electron system in the molecule. The electrochemical investigation indicated that the electron in the FVHC may partially be delocalized over the π-conjugated system and CT process in functionalized carbazole systems. Besides, the compound exhibited strong UV absorption and large optical limiting effect, indicating promising potential applications as useful OL materials.
Co-reporter:Hong-Ping Zhou, Dong-Mei Li, Ju-Zhou Zhang, Yong-Min Zhu, Jie-Ying Wu, Zhang-Jun Hu, Jia-Xiang Yang, Gui-Bao Xu, Yu-Peng Tian, Yi Xie, Xu-Tang Tao, Min-Hua Jiang, Li-Min Tao, Ya-Hui Guo, Chuan-Kui Wang
Chemical Physics 2006 Volume 322(Issue 3) pp:459-470
Publication Date(Web):20 March 2006
DOI:10.1016/j.chemphys.2005.09.045
Abstract
Three novel A–π–D–π–A type compounds 3,6-bis[2-(4-pyridyl)ethenyl]-9-ethylcarbazole (1), 3,6-bis[2-(2-pyridyl)ethenyl]-9-ethylcarbazole (2), 3,6-bis[2-(4-pyridyl)ethenyl]-9-ethylpyridylcarbazole (3) were conveniently synthesized by Pd-catalyzed Heck coupling methodology and characterized by single crystal X-ray diffraction determination. One-photon fluorescence, one-photon fluorescence quantum yields, one-photon fluorescence lifetime, and two-photon fluorescence have been investigated. The calculated two-photon absorption cross-sections for the three initiators by quantum chemical method are as high as 947, 943 and 815 × 10−50 cm4 s photon−1, respectively. Two-photon initiating polymerization microfabrication experiments have been carried out and the possible polymerization mechanism was also discussed. The results show that they are good two-photon absorbing chromophores and effective two-photon photopolymerization initiators.
Co-reporter:Hong-Ping Zhou;Jie-Ying Wu;Ju-Zhou Zhang;Dong-Mei Li;Yong-Min Zhu;Zhang-Jun Hu;Xu-Tang Tao;Min-Hua Jiang;Yi Xie
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 24) pp:
Publication Date(Web):27 OCT 2005
DOI:10.1002/ejic.200500439
Two novel functional rigid ligands, 2,2′- and 4,4′-bipyridyl-based “building blocks”, 9-ethyl-3,6-bis[2-(4-pyridyl)ethenyl]carbazole (L1) and 9-ethyl-3,6-bis[2-(2-pyridyl)ethenyl]carbazole (L2), were synthesized. Treatment of L1,2 as “building blocks” with Hg(SCN)2 or HgI2 afforded helixes, macrocycles, and chains, which can be further self-assembled by a π–π stacking interaction, hydrogen bond, and interatomic force in the solid state to form two-dimensional networks. In complexes 1–4, HgII centers all adopt four-coordination modes in different coordination environments, but they present different architectures with slightly adjusted structures of the ligands and counteranions, indicating that the nature of the ligand and anion plays an important role in the coordination networks. The luminescent properties of compounds 1–4 have been studied.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Hong-Ping Zhou, Ju-Zhou Zhang, Dong-Mei Li, Yong-Min Zhu, Zhang-Jun Hu, Jie-Ying Wu, Yi Xie, Min-Hua Jiang, Xu-Tang Tao, Yu-Peng Tian
Journal of Molecular Structure 2005 Volume 743(1–3) pp:93-96
Publication Date(Web):31 May 2005
DOI:10.1016/j.molstruc.2005.01.073
A novel double helix coordination polymer, [Cd(2,2′-bpeec)I2]n (1) (2,2′-bpeec=3,6-bis[2-(2-pyridyl)ethenyl]-9-ethylcarbazole) has been prepared and characterized by elemental analyses, IR and luminescence spectra, single crystal X-ray diffraction. Complex 1 crystallizes in the space group P21/c with a=8.444(2), b=23.126(4), c=14.156(2), β=97.927(2), Z=4, V=2737.8(7) Å3, μ=3.073 mm−1. The 2D framework of the title compound is formed by C–H⋯I hydrogen bonds and π–π interactions. The solid-state fluorescent analyses show that the compound exhibits a broad emission band at 547 nm.
Co-reporter:Dong-Mei Li;Hong-Ping Zhou;Ji-Qin Pu;Xiao-Jun Feng;Jie-Ying Wu;Xiao-Qiang Yu;Xu-Tang Tao;Min-Hua Jiang
Chinese Journal of Chemistry 2005 Volume 23(Issue 11) pp:
Publication Date(Web):30 NOV 2005
DOI:10.1002/cjoc.200591483
The synthesis, luminescence and electrochemical properties of two novel phenothiazine derivatives were presented, which exhibit good one-photon fluorescence emission. The quantum yields and solvent effects of them were studied in detail. Compound 3,7-bis(2-4′-imidazolylbenzylidenehydrazonoethyl)-(0-ethylphenothiazine) (5) was used as an effective initiator, of which two-photon fluorescence spectra were investigated under 800 nm fs laser pulse and the measured two-photon absorption cross-section was 18×10−50 cm4·s per photon. Two-photon initiated polymerization microfabrication experiments were carried out. X-ray diffraction analyses revealed that the shape of the compound 3,7-bis(2-pyrid-4′-ylmethylidenehydrazonoethyl)-(0-ethylphenothiazine) (4) looks like a butterfly with nearly planar wings. The dihedral angle of the two benzene rings is 37.6° and there is an obvious π-π stacking interaction between the molecules in the crystal.
Co-reporter:Yang Jia-Xiang;Hu Zhang-Jun;Zhang Ze;Tian Yu-Peng;Liu Qing-Liang;Chantrapromma Suchada;Fun Hoong-Kun
Chinese Journal of Chemistry 2005 Volume 23(Issue 5) pp:
Publication Date(Web):14 JUN 2005
DOI:10.1002/cjoc.200590533
Two new complexes [Zn2(phen)4(FCA)2](ClO4)2·(H2O)2 (1) and [Co2(phen)4 (FCA)2](ClO4)2·(H2O)2 (2) (FCA=anion of 3-ferrocenyl-2-crotonic acid, phen=1,10-phenanthroline) have been synthesized, and characterized by elemental analysis, IR, UV-Vis spectra, thermal analyses, and single-crystal X-ray diffraction. Two M(II) (M=Zn or Co) ions are bridged by two FCA anions with syn-anti bridging ligands, leading to dimeric cores, [M2(phen)4(FCA)2]2+, and each M(II) ion is six-coordinated in a distorted octahedral geometry by two chelate phen ligands and two μ2-carboxylate oxygen atoms from two FCA groups. The M(II)…M(II) intradimer distances are 0.4391 and 0.4462 nm in 1 and 2, respectively. Electrochemical properties of the complexes have been discussed.
Co-reporter:Zhao-Ming Xue, Yu-Peng Tian, Dong Wang and Min-Hua Jiang
Dalton Transactions 2003 (Issue 7) pp:1373-1378
Publication Date(Web):28 Feb 2003
DOI:10.1039/B301589K
A new ligand, 4-dipropylaminobenzaldehyde thiosemicarbazone (HL) and its complexes (ZnL2, CdL2), which exhibit intense two-photon excited (TPE) dual fluorescence using 800 nm laser pulses in the femtosecond regime, were synthesized and fully characterized. The measured power dependence of the fluorescence signals provides direct evidence for TPE. The two-photon excited dual fluorescence spectra were compared and contrasted with the corresponding results obtained from one-photon excitation. Emission peaks of the ligand and its complexes were assigned with the aid of PM3 calculations.
Co-reporter:Chunxia Fang, Shengyi Zhang, Pengfei Zuo, Wei Wei, Baokang Jin, Jieying Wu, Yupeng Tian
Journal of Crystal Growth (1 April 2009) Volume 311(Issue 8) pp:2345-2351
Publication Date(Web):1 April 2009
DOI:10.1016/j.jcrysgro.2009.02.003
Ortho-CuAgSe nanotubes were facilely synthesized through a nanotube–nanotube transformation process in aqueous solution at room temperature. The products as-obtained were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDX), X-ray photoelectron spectra (XPS) and thermogravimetric (TG)/differential scanning calorimetric (DSC). On the basis of a series of the experiment results, the formation mechanism of ortho-CuAgSe nanotubes was proposed. From kinetics and energetics, it had been demonstrated that the exchange of univalent cation between ortho-Ag2Se (orthorhombic phase Ag2Se) nanotubes and ortho-Cu2Se nanotubes in the formation process of ortho-CuAgSe nanotubes was feasible in mild condition. Furthermore, the electrochemical property of the nanotubes as-obtained was studied by the voltammetric technique.
Co-reporter:Lin Li, Yupeng Tian, Jiaxiang Yang, Pingping Sun, Lin Kong, Jieying Wu, Hongping Zhou, Shengyi Zhang, Baokang Jin, Xutang Tao and Minhua Jiang
Chemical Communications 2010 - vol. 46(Issue 10) pp:NaN1675-1675
Publication Date(Web):2010/01/11
DOI:10.1039/B918841J
The accurate photophysical data of dye-concentrated nanoparticles have been measured by the strategy of constructing ethoxysilane hydrolysis-assisted nanomaterials, which give rise to a large enhancement in two-photon absorption.
Co-reporter:Dandan Li, Xiaohe Tian, Aidong Wang, Lijuan Guan, Jun Zheng, Fei Li, Shengli Li, Hongping Zhou, Jieying Wu and Yupeng Tian
Chemical Science (2010-Present) 2016 - vol. 7(Issue 3) pp:NaN2263-2263
Publication Date(Web):2015/12/21
DOI:10.1039/C5SC03956H
Rational design of specific ratiometric viscosity probes with small molecular weight is a challenge in practical biotechnology applications. Herein two novel water-soluble, small-molecular ratiometric probes, bearing N-methyl benzothiazolium moiety (DSF and DBF), are designed for two-photon fluorescent imaging as a functional of local viscosity. The dye DSF, a light-up fluorescent probe, is sensitive to local viscosity and selectively stains nuclear DNA, which can be used to inspect asynchronous cells under confocal microscopy. While the dye DBF as a molecular rotor displays strong fluorescence enhancement in viscous media or binding to RNA. It exhibits dual absorption and emission as well, and only the red emission is markedly sensitive to viscosity changes, providing a ratiometric response and selectively imaging nucleolic and cytosolic RNA. Interestingly it is shown, for the first time, that the intracellular targeting and localization (DNA and RNA) of the two dyes are entirely realized simply by modifying the substituent attached to the benzothiazolium.
Co-reporter:Pengfei Shi, Qin Jiang, Sergio Sánchez, Xuesong Zhao, Qiong Zhang and Yupeng Tian
Dalton Transactions 2015 - vol. 44(Issue 30) pp:NaN13760-13760
Publication Date(Web):2015/07/07
DOI:10.1039/C5DT90118A
Correction for ‘Study of the one-photon and two-photon properties of two water-soluble terpyridines and their zinc complexes’ by Pengfei Shi et al., Dalton Trans., 2015, 44, 8041–8048.
Co-reporter:Cuiyun Nie, Qiong Zhang, Hongjuan Ding, Bei Huang, Xinyan Wang, Xianghua Zhao, Shengli Li, Hongping Zhou, Jieying Wu and Yupeng Tian
Dalton Transactions 2014 - vol. 43(Issue 2) pp:NaN608-608
Publication Date(Web):2013/09/24
DOI:10.1039/C3DT51318A
To explore the photophysical properties of coordination compounds with enhanced two-photon absorption, two novel six-coordinated metal complexes (ML2, M = Cd(II), Zn(II)) from carbazole β-diketone ligand (HL = 4,4,4-trifluoro-1-(9-butylcarbazole-3-yl)-1,3-butanedione) were prepared and fully characterized. Their crystal structures were determined by X-ray diffraction analysis. Both variable temperature 1H NMR spectra and MALDI-TOF mass spectrometry proved that the coordination compounds exhibit good stability in solution. The results of time-dependent density functional theory (TD-DFT) calculations indicated that the complexation of the ligands with metal ion extends the electronic delocalization in the coordination compounds, leading to enhanced two-photon absorption. The photophysical properties for the coordination compounds were identified relying on both experimentally and theoretically studies. Finally, confocal microscopy and two-photon microscopy fluorescent imaging of HepG2 cells labeled with the Zn(II) complexe revealed its potential applications as a biological fluorescent probe.
Co-reporter:Qiong Zhang, Xiaohe Tian, Zhangjun Hu, Caroline Brommesson, Jieying Wu, Hongping Zhou, Shengli Li, Jiaxiang Yang, Zhaoqi Sun, Yupeng Tian and Kajsa Uvdal
Journal of Materials Chemistry A 2015 - vol. 3(Issue 36) pp:NaN7221-7221
Publication Date(Web):2015/08/06
DOI:10.1039/C5TB01185J
It is still a challenge to obtain two-photon excited fluorescent bioimaging probes with intense emission, high photo-stability and low cytotoxicity. In the present work, four Zn(II)-coordinated complexes (1–4) constructed from two novel D–A and D–π–A ligands (L1 and L2) are investigated both experimentally and theoretically, aiming to explore efficient two-photon probes for bioimaging. Molecular geometry optimization used for theoretical calculations is achieved using the crystallographic data. Notably, the results indicate that complexes 1 and 2 display enhanced two-photon absorption (2PA) cross sections compared to their corresponding D–A ligand (L1). Furthermore, it was found that complex 1 has the advantages of moderate 2PA cross section in the near-infrared region, longer fluorescence lifetime, higher quantum yield, good biocompatibility and enhanced two-photon excited fluorescence. Therefore, complex 1 is evaluated as a bioimaging probe for in vitro imaging of HepG2 cells, in which it is observed under a two-photon scanning microscope that complex 1 exhibits effective co-staining with endoplasmic reticulum (ER) and nuclear membrane; as well as for in vivo imaging of zebrafish larva, in which it is observed that complex 1 exhibits specificity in the intestinal system.
Co-reporter:Ming Kong, Ting Wang, Xiaohe Tian, Fang Wang, Yanqiu Liu, Qiong Zhang, Hui Wang, Hongping Zhou, Jieying Wu and Yupeng Tian
Journal of Materials Chemistry A 2015 - vol. 3(Issue 21) pp:NaN5588-5588
Publication Date(Web):2015/04/20
DOI:10.1039/C5TC00716J
A series of asymmetrical D–π–D type thiophene-based chromophores with small sizes and different electron-donating groups were designed and synthesized in high yield. Single-crystal X-ray diffraction analysis and theoretical calculations were carried out to further explore the electronic structural features of the chromophores. It was observed that multiple C–H⋯π interactions and C–H⋯O hydrogen bonds played an important role in crystal stacking. Systematic investigations, including fluorescence quantum yields, fluorescence lifetime, and two-photon absorption (2PA) cross sections, revealed that the photophysical properties of the thiophene-based chromophores can be tunable by the modulation of electron-donating terminal units. Furthermore, by introducing a carbonyl group in the π-bridge center, one of the chromophores with a small size exhibited significantly enhanced two-photon absorption with a 36-fold increase of the 2PA cross section compared with that of the corresponding chromophore. Finally, due to their superior 2PA character in the near-infrared region (700–900 nm), two-photon excited bioimaging applications were carried out for the chromophores. The results of live cell imaging experiments showed that the chromophores can be effectively penetrated into the cytosol of HepG2 cells and their physiological activity can be detected in vitro using two-photon fluorescence microscopy.
Co-reporter:Rui Ke, Xiaomei Zhang, Shengyi Zhang, Shengli Li, Changjie Mao, Helin Niu, Jiming Song and Yupeng Tian
Physical Chemistry Chemical Physics 2015 - vol. 17(Issue 41) pp:NaN27557-27557
Publication Date(Web):2015/09/22
DOI:10.1039/C5CP04419G
A facile one-step method for the synthesis of a water-soluble selenium/polypyrrole (Se/PPy) nanocomposite was developed. In the aqueous synthesis process, the pyrrole acted as a reductant for the reduction of H2SeO3, and then the elemental Se formed in situ acted as a catalyst for the polymerization of pyrrole. The characterization results show that the as-obtained composite (Se/PPy) is a spherical (Φ80 nm) product that is made up of amorphous Se particles coated by PPy layers. The formation mechanism and influence factors of the products were discussed, based on a series of experiments. It is proposed that remainder H2SeO3 adsorbed on the PPy chains increased the water-solubility and conductivity of the Se/PPy nanocomposite. Significantly, relying on the synergistic effect of photo-conductive Se nanoparticles and electric-conductive PPy molecules, the Se/PPy nanocomposite possesses a large two-photon absorption (2PA) cross-section and good optical limiting properties, which were demonstrated by the Z-scan technique using a femtosecond laser. We believe that this work should be an interesting strategy for developing polymer composites with excellent optoelectrical properties.
Co-reporter:Xiaohe Tian, Yingzhong Zhu, Mingzhu Zhang, Lei Luo, Jieying Wu, Hongping Zhou, Lijuan Guan, Giuseppe Battaglia and Yupeng Tian
Chemical Communications 2017 - vol. 53(Issue 23) pp:NaN3306-3306
Publication Date(Web):2017/02/15
DOI:10.1039/C6CC09470H
We present a two-photon (2P, 800 nm) PDT cyclometalated Iridium(III) complex (Ir-Es) that targets the intracellular nucleus. The complex is capable of migrating sequentially from the nucleus to mitochondria and inducing dual-damage under light exposure. This study suggests that with minor modification of the terminal moieties of complexes, their final intracellular destinations and PDT efficiency can be significantly impacted.
Co-reporter:Xiaohe Tian, Yingzhong Zhu, Qiong Zhang, Ruilong Zhang, Jieying Wu and Yupeng Tian
Chemical Communications 2017 - vol. 53(Issue 56) pp:NaN7944-7944
Publication Date(Web):2017/06/22
DOI:10.1039/C7CC03640J
We reported a simple and universal strategy by tuning halides (Cl, Br and I) in terpyridine–Zn(II) complexes to achieve different subcellular organelle targeting (nucleolus, nucleus and intracellular membrane systems, respectively) via different cellular uptake mechanisms, resulting from halide triggering different polymorphs of these complexes.
Co-reporter:Xiaohe Tian, Yingzhong Zhu, Qiong Zhang, Ruilong Zhang, Jieying Wu and Yupeng Tian
Chemical Communications 2017 - vol. 53(Issue 56) pp:NaN7944-7944
Publication Date(Web):2017/06/22
DOI:10.1039/C7CC03640J
We reported a simple and universal strategy by tuning halides (Cl, Br and I) in terpyridine–Zn(II) complexes to achieve different subcellular organelle targeting (nucleolus, nucleus and intracellular membrane systems, respectively) via different cellular uptake mechanisms, resulting from halide triggering different polymorphs of these complexes.
Co-reporter:Yu-Peng Tian, Lin Li, Ju-Zhou Zhang, Jia-Xiang Yang, Hong-ping Zhou, Jie-ying Wu, Ping-ping Sun, Li-min Tao, Ya-hui Guo, Chuan-Kui Wang, Hui Xing, Wen-hao Huang, Xu-Tang Tao and Min-Hua Jiang
Journal of Materials Chemistry A 2007 - vol. 17(Issue 34) pp:NaN3654-3654
Publication Date(Web):2007/07/02
DOI:10.1039/B703853D
Six centrosymmetric D–(π–A)3 structural triphenylamine derivatives that can be used as two-photon photopolymerization and optical data storage chromophores, tris[4-(4-pyridylethenyl)phenyl]amine (1), tris[4-(2-pyridylethenyl)phenyl]amine (2), tris(4-cyanoethenylphenyl)amine (3), tris[4-butylacrylatephenyl]amine (4), tris[4-methylacrylatephenyl]amine (5) and tris[4-acrylicethenylphenyl]amine (6), have been successfully synthesized via a triple palladium-catalyzed Heck coupling reaction, and the novel chromophores were fully characterized by elemental analysis, IR, 1H-NMR and ESIMS. The structure for 3 was determined by single crystal X-ray diffraction study. One- and two-photon absorption and fluorescence in various solvents were experimentally investigated. Two-photon initiated polymerization microfabrication and optical data recording experiments were carried out under 780 nm laser radiation, and the possible polymerization mechanism is discussed based on theoretical calculations. All the six chromophores have relatively large two-photon absorption cross-sections, and exhibit optical memory and highly efficient two-photon initiated polymerization abilities.
Co-reporter:Fuying Hao, Xuanjun Zhang, Yupeng Tian, Hongping Zhou, Lin Li, Jieying Wu, Shengyi Zhang, Jiaxiang Yang, Baokang Jin, Xutang Tao, Guangyong Zhou and Minhua Jiang
Journal of Materials Chemistry A 2009 - vol. 19(Issue 48) pp:NaN9169-9169
Publication Date(Web):2009/10/23
DOI:10.1039/B914656C
A new series of hybrid dyes, trans-4-(4′-N,N-dialkylaminostyryl)-N-methyl pyridinium [Cd(SCN)3−]n [alkyl = Me(1), Et(2), Pr(3) and n–Bu(4)] have been successfully synthesized from hybrids of inorganic polymers and organic chromophores. The structures of four new hybrid dyes were characterized by single-crystal X-ray diffraction first. The particular features of the hybrid dyes are (1) the inorganic anions form isolated polymeric one-dimensional zig-zag chains of [Cd(SCN)3−]n with an extended π-conjugation system within the polymeric –[M–S–C≡N]–M… chain and high polarizabilities; and (2) the organic cationic chromophores determine their optical properties. Experimental results revealed that the TPA cross-section values and overall energy conversion efficiencies of hybrid dyes with different alkyl pendant groups have obviously increased from 1 to 4, and in particular, have been substantially enhanced compared to their corresponding iodide analogues 1′–4′. Therefore, we speculate that such increases are attributable to arrangements of infinite anionic [Cd(SCN)3−]n chains and synergic effects with chromophore cations.
Co-reporter:Lin Kong, Jiaxiang Yang, Xiaopeng Hao, Hongping Zhou, Jieying Wu, Fuying Hao, Lin Li, Shengyi Zhang, Baokang Jin, Xutang Tao, Minhua Jiang and Yupeng Tian
Journal of Materials Chemistry A 2010 - vol. 20(Issue 35) pp:NaN7377-7377
Publication Date(Web):2010/07/27
DOI:10.1039/C0JM00004C
A carbazole derivative (3-(2,2-dicyanovinyl)-9-hexylcarbazole, abbreviated as L) has been designed, synthesized and used to prepare a novel organic–inorganic nanohybrid consisting of silver nanocrystals (Ag NCs) uniformly dispersed on the surface of L nanoribbons. Detailed characterizations have been performed. The results reveal that L couples with Ag NCs through a π-conjugated unit, which results in a significant red-shift of the fluorescence (FL), an obvious increase of FL lifetime and enhanced Raman scattering.
Co-reporter:Lin Kong, Jia-xiang Yang, Zhao-ming Xue, Hong-ping Zhou, Long-jiu Cheng, Qiong Zhang, Jie-ying Wu, Bao-kang Jin, Sheng-yi Zhang and Yu-peng Tian
Journal of Materials Chemistry A 2013 - vol. 1(Issue 33) pp:NaN5057-5057
Publication Date(Web):2013/06/07
DOI:10.1039/C3TC30515E
A D–π–A type phenothiazine derivative 4-((E)-2-(10-ethyl-10H-phenothiazin-3-yl)-vinyl)-benzaldehyde (abbreviated as L) was designed, synthesized and characterized by single crystal X-ray diffraction analysis. Dispersion-corrected theoretical calculation revealed that L molecules tend to grow along a 1-dimensional (1-D) orientation. Further, L was used to prepare nanohybrids consisting of silver nanoparticles (NPs) dispersed on L nanoribbons. L molecules coupled with Ag NPs through S atoms, which brought about a significant blue-shift of the fluorescence (FL) and an obvious increase of FL lifetime. Through fluorescence microscopy, the spectral change was used as a wavelength-based biodetection tool to study the possible mechanism for an enhanced inhibitory effect of L–Ag nanohybrids on both gram-negative bacterium Escherichia coli and gram-positive bacterium Staphylococcus aureus compared to either pure Ag NPs or pure L.
Co-reporter:Lin Kong, Yu-peng Tian, Qi-yu Chen, Qiong Zhang, Hui Wang, Dong-qin Tan, Zhao-ming Xue, Jie-ying Wu, Hong-ping Zhou and Jia-xiang Yang
Journal of Materials Chemistry A 2015 - vol. 3(Issue 3) pp:NaN581-581
Publication Date(Web):2014/11/05
DOI:10.1039/C4TC01605J
A D–π–A type triphenylamine derivative (E)-3-(4-(4-(diphenylamino)styryl)-phenyl)acrylonitrile (abbreviated as L) is designed, synthesized and characterized by single crystal X-ray diffraction analysis, which is demonstrated to exhibit superior AIEE (aggregation-induced enhanced emission) properties. Self-aggregates of L obtained with and without the guidance of metal ions (Cd2+ or Cu2+) showed morphology-dependent luminescent properties. The coupling and synergy effects between L and metal ions bring about an energy transfer process between the components, which further results in red-shifted absorption and fluorescence, an enhanced fluorescent quantum yield and tunable FL lifetime. The interactions between L and metal ions also change nonlinear optical properties, including two-photon excited fluorescence (2PEF), two-photon absorption (2PA) cross-section (δ), two-photon action cross-section (ηδ) and two-photon absorption coefficient (β), which further leads to successful application of the samples as a two-photon fluorescent probe for labelling the intercellular section. The study indicates that the preparation of nanohybrids from metal ions and an AIEE organic compound is a promising method to prepare 2PA probes possessing a high ηδ for biological imaging.
Co-reporter:Yanqiu Liu, Ming Kong, Qiong Zhang, Zhiwen Zhang, Hongping Zhou, Shengyi Zhang, Shengli Li, Jieying Wu and Yupeng Tian
Journal of Materials Chemistry A 2014 - vol. 2(Issue 33) pp:NaN5440-5440
Publication Date(Web):2014/07/15
DOI:10.1039/C4TB00464G
A specific series of D–π–A (1A–3A) and D–π–A (1B–3B) structural chromophores with various electron donors and π-conjugated bridges were designed, synthesized, and fully characterized. Their crystal structures were determined by single crystal X-ray diffraction analysis. The one/two-photon absorption properties of the chromophores have been successfully tuned by using different electron donors and π-bridges. Interestingly, it was found that chromophore 3B shows quite weak fluorescence in pure DMSO, while a significant AIE (aggregation-induced emission) effect is observed in water–DMSO (v/v 90%) mixtures with a sharp increase in fluorescence intensity of about 11 times. Furthermore, chromophore 3B shows strong two-photon excited fluorescence (TPEF) and has a large 2PA action cross-section (394 GM). The results of live-cell imaging experiments show that 3B can be effectively used as a bio-imaging probe in two-photon fluorescence microscopy towards HepG2 cells in vitro. The TPEF images of 3B not only exhibit cellular cytosol uptake but also exhibit actin regulatory protein uptake which are different from OPEF images.
Co-reporter:Hui Wang, Xiaohe Tian, Lijuan Guan, Qiong Zhang, Shengyi Zhang, Hongping Zhou, Jieying Wu and Yupeng Tian
Journal of Materials Chemistry A 2016 - vol. 4(Issue 17) pp:NaN2902-2902
Publication Date(Web):2016/04/01
DOI:10.1039/C6TB00433D
As a semi-autonomous organelle, the eukaryotic mitochondrion possesses an individual DNA and protein synthesizing system. Therefore, the mitochondrial DNA-targeting probes are powerful tools to understand the functions in physiological processes. Herein, we report a novel Ru(II) complex (HLRu) based on a phenanthroline derivative to target mitochondrial DNA. The nonlinear optical property study revealed a reverse nonlinear optical refraction character from self-focusing to self-defocusing response before and after complexation with Ru(II). Furthermore, the two-photon absorption and high biocompatibility of complex HLRu highlight its potential applications in biological processes. It was found that complex HLRu specifically binds to mitochondrial DNA in living cells and enables imaging of tissues with minimal auto-fluorescence. As a result, this complex HLRu probe offers a promising platform to directly monitor mitochondrial DNA in living cells.
Co-reporter:Qiong Zhang, Lin Li, Man Zhang, Zhaodi Liu, Jieying Wu, Hongping Zhou, Jiaxiang Yang, Shengyi Zhang and Yupeng Tian
Dalton Transactions 2013 - vol. 42(Issue 24) pp:NaN8853-8853
Publication Date(Web):2013/04/08
DOI:10.1039/C3DT50582K
Biological metal detecting, small molecule probes bearing nonlinear optical (NLO) response provide powerful alternatives due to their favorable photophysical properties (e.g. excitation wavelength in the near-IR region), cell permeability (due to their size), and chemical structure flexibility. Here, we present a series of pyrimidine-based NLO biological metal probes, especially a novel copper specific one which taken into account of the small volume-scaled and low cost-scaled nonlinear optical response of TPP and TPP–Cu2+ discussed in our present work. The photophysical properties of the probes were thoroughly investigated. 1H NMR and theoretical computation prove the binding interaction between the probe and the copper ion, which supports the functions of the molecule as a fluorescence signaling unit showing strong fluorescence quenching upon copper metal ion binding. On the other hand, the two-photon absorption cross-section of the novel copper probe increased from 275 to 591 GM (λex = 830 nm) after interacting with copper ion. It was further demonstrated that the NLO response for the copper(II) ion probe could be used for biological copper detection in live cells.
Co-reporter:Qiong Zhang, Yuanhao Gao, Shengyi Zhang, Jieying Wu, Hongping Zhou, Jiaxiang Yang, Xutang Tao and Yupeng Tian
Dalton Transactions 2012 - vol. 41(Issue 23) pp:NaN7072-7072
Publication Date(Web):2012/04/05
DOI:10.1039/C2DT30622K
A novel sulfur-terminal Cd(II) complex, CdS2L (L = N-hexyl-3-{2-[4-(2,2′:6′,2′′-terpyridin-4′-yl)phenyl]ethenyl}-carbazole), was successfully synthesized from CdS nanocrystals and the organic chromophores (L), which was confirmed by single-crystal X-ray diffraction analysis. Its photophysical properties have been investigated both experimentally and theoretically. The novel hybrid nanoparticles (CdS/L) were then obtained using the L as surface capped agent, which aggregate into large spheres, exhibiting novel luminescent properties, strong two photon absorption (TPA) and obvious prolonged fluorescence lifetime, which differ from those of the pure CdS nanocrystals and free L.
Co-reporter:Pengfei Shi, Qin Jiang, Xuesong Zhao, Qiong Zhang and Yupeng Tian
Dalton Transactions 2015 - vol. 44(Issue 17) pp:NaN8048-8048
Publication Date(Web):2015/03/19
DOI:10.1039/C5DT00449G
Two water soluble 2,2′:6′,2′′-terpyridine derivatives (TPYOH and O3TPY) with a di(hydroxyethyl)amino or a long (2-(2-methoxyethoxy)ethoxy)benzyl group, respectively, were designed and synthesized. The two terpyridine ligands and their Zn(II) complexes display strong one-photon fluorescence. An unusually large solvatochromism effect in ethanol and water was found, which was ascribed to their interactions with the solvent through hydrogen bonds. All the four compounds show evident two-photon absorption ability when evaluated by Z-scan technology. The free ligands could give distinct two-photon excited fluorescence, and the emission of O3TPY responded linearly with Zn2+ under the excitation of a 780 nm femtosecond laser. Only the complex ZnO3TPY, which possesses a large π conjugation system and suitable election-donating groups, displayed emission maxima at 595 nm when excited by a 680–880 nm laser.
Co-reporter:Jingyun Tan, Rui Li, Dandan Li, Qiong Zhang, Shengli Li, Hongping Zhou, Jiaxiang Yang, Jieying Wu and Yupeng Tian
Dalton Transactions 2015 - vol. 44(Issue 3) pp:NaN1482-1482
Publication Date(Web):2014/11/12
DOI:10.1039/C4DT02933J
A novel 4′-(4-(diphenylamino)thienyl)-2,2′:6′,2′′-terpyridine ligand (L) based on thiophene and its LZnX2 complexes (X = Cl, Br, I, SCN) was designed, synthesized and characterized by elemental analysis, far-IR, MALDI-TOF-MS, and single crystal X-ray diffraction analysis. Structural studies revealed that the central zinc(II) atom adopted a distorted trigonal bipyramidal coordination model. However, there were different hydrogen bonds and stacking models with different counter anions in the crystals. The absorption properties of the compounds were investigated with the aid of TD-DFT computational methods. Furthermore, the third-order nonlinear optical (NLO) properties were systematically studied via open-aperture Z-scan methods using a tunable wavelength femtosecond laser. The results from photophysical property investigations suggested that the complexation of the thiophene-based terpyridine ligand with zinc halides resulted in strong ICT/LLCT bands of about 450 nm, and the complexes exhibited strong nonlinear optical response in the near-infrared range around 850 nm. Above all, the two-photon absorption (2PA) cross-section values (σ) were enhanced by coordination with zinc and influenced by halide ions, reaching up to 2583 GM (X = Br).
Co-reporter:Xuesong Zhao, Jie Liu, Hui Wang, Yan Zou, Shengli Li, Shengyi Zhang, Hongping Zhou, Jieying Wu and Yupeng Tian
Dalton Transactions 2015 - vol. 44(Issue 2) pp:NaN709-709
Publication Date(Web):2014/11/03
DOI:10.1039/C4DT02251C
Three novel organooxotin complexes (Z1, Z2 and Z3) were synthesized by reaction of L1 (2-cyano-3-(4-(diphenylamino)phenyl) acrylic acid) with n-Bu2SnO, Ph3Sn(OH) and nBu6Sn2O. The structures of the three complexes have been confirmed by single-crystal X-ray diffraction analysis. The metal complex Z1 features a ladder framework while Z2 and Z3 show discrete structures. The UV-vis absorption, single-photon excited fluorescence (SPEF) and two-photon excited fluorescence (2PEF) of the complexes have been systematically studied, suggesting that the three metal complexes have strong two-photon absorption (2PA) and large 2PA cross-sections. It is noteworthy that Z2 possesses an enhanced two-photon absorption, and Z3 exhibits larger 2PA cross-section per molecular weight compared to L1. Finally, high anti-tumor activity of these three metal complexes has also been identified.
Co-reporter:Zhang-Jun Hu, Xiao-He Tian, Xiang-Hua Zhao, Peng Wang, Qiong Zhang, Ping-Ping Sun, Jie-Ying Wu, Jia-Xiang Yang and Yu-Peng Tian
Chemical Communications 2011 - vol. 47(Issue 46) pp:NaN12469-12469
Publication Date(Web):2011/10/28
DOI:10.1039/C1CC14968G
A novel europium(III) β-diketonate complex exhibiting bright two-photon-sensitized luminescence is synthesized and applied as a two-photon-sensitized luminescent probe to stain DNA in live cells.
Co-reporter:Xiaohe Tian, Qiong Zhang, Mingzhu Zhang, Kajsa Uvdal, Qin Wang, Junyang Chen, Wei Du, Bei Huang, Jieying Wu and Yupeng Tian
Chemical Science (2010-Present) 2017 - vol. 8(Issue 1) pp:NaN149-149
Publication Date(Web):2016/08/03
DOI:10.1039/C6SC02342H
Small, biocompatible and water-soluble molecules with high two-photon absorption (2PA) cross-section values (δ) are in high demand for specific bioimaging applications. Here, two novel terpyridine derivative ligands with donor–acceptor (D–A) (L1) and donor–π–acceptor (D–π–A) (L2) models, and their corresponding Zn(II) complexes are designed and characterized. It was found that the two-photon absorption cross section values (δ) in the near-infrared region (NIR, about 800 nm) are significantly enhanced for complexes 1 and 2 compared to their free D–A type ligand L1, while those of complexes 3 and 4 were greatly decreased relative to their free ligand L2, thus confirming that the smaller ligand (D–A type) displays a suitable Turn-ON fluorescence pair for two-photon fluorescence microscopy (2PFM). Firstly, the potential of simultaneously labeling a live cell plasma membrane and nucleus using complex 1 is demonstrated. In addition, live larval and adult zebrafish incubated with an optimal concentration of 1 demonstrated clear brain uptake. Lastly and importantly, using such a probe to visualize the blood–brain-barrier (BBB) capillary endothelial cells and penetrate the BBB into the central nervous system (CNS) intravenously in a mouse model is also explored.
Co-reporter:Jian Su, Jun Zhang, Xiaohe Tian, Meng Zhao, Tao Song, Jiancan Yu, Yuanjing Cui, Guodong Qian, Hong Zhong, Lei Luo, Yujin Zhang, Chuankui Wang, Shengli Li, Jiaxiang Yang, Hongping Zhou, Jieying Wu and Yupeng Tian
Journal of Materials Chemistry A 2017 - vol. 5(Issue 27) pp:NaN5463-5463
Publication Date(Web):2017/06/16
DOI:10.1039/C6TB03321K
How can imaging be improved? Coordination polymers (CPs) show fascinating potential in optoelectronic optics but limited potential in bioimaging. Without doubt, it was very meaningful when CPs were first used in second-harmonic generation (SHG) imaging. Herein, through reasonable design and synthesis, a series of nonlinear optical CPs bearing very good one-photon excited fluorescence (OPEF), two-photon excited fluorescence (TPEF) and very strong SHG properties has been presented. Further study demonstrated that the nanoscale CPs show very strong SHG signals which have been applied in the three-dimensional imaging of thick block tissue with higher spatial resolution through simultaneous multichannel nonlinear optical (NLO) imaging technology. After simple encapsulation by polymeric micelles, the nanoscale CPs were successfully applied in SHG bio-imaging within the living cells. This finding throws light on the design of nanoscale NLO CPs and offers a simple avenue to develop novel effective exogenous SHG imaging agents.
Co-reporter:Yingzhong Zhu, Wei Du, Mingzhu Zhang, Ying Xu, Leilei Song, Qiong Zhang, Xiaohe Tian, Hongping Zhou, Jieying Wu and Yupeng Tian
Journal of Materials Chemistry A 2017 - vol. 5(Issue 21) pp:NaN3869-3869
Publication Date(Web):2017/04/22
DOI:10.1039/C7TB00726D
It is believed that HSO3− and SO32− play important roles in several physiological processes. However, probes with two-photon absorption to detect HSO3− or SO32− in living cells are still limited. Herein, a series of novel indolium derivatives (L1–L4) with an A–π–A′ structure was designed and synthesized as ratiometric probes to detect HSO3−/SO32−in vitro. L3 and L4 display a colorimetric and ratiometric fluorescence dual response to HSO3−/SO32− with a very fast (∼15 s) and high specificity, as well as low detection limits (∼22 nM). Furthermore, their detection is also carried out by using a two-photon excited fluorescence method. A nucleophilic addition reaction is proposed for the sensing mechanism, which is supported by MS, 1H NMR, and density functional theory (DFT) investigations. Importantly, L3 was successfully used for detecting intrinsically generated intracellular HSO3−/SO32− in cancerous cells under one- and two-photon excited fluorescence imaging.
Co-reporter:Meng Zhao, Yingzhong Zhu, Jian Su, Qian Geng, Xiaohe Tian, Jun Zhang, Hongping Zhou, Shengyi Zhang, Jieying Wu and Yupeng Tian
Journal of Materials Chemistry A 2016 - vol. 4(Issue 35) pp:NaN5912-5912
Publication Date(Web):2016/07/29
DOI:10.1039/C6TB01240J
A convenient and rationally designed water-soluble two-photon excited fluorescence (TPEF) sensor for monitoring viscosity with specific targeting at the subcellular level remains a challenge. Herein, we reported a novel water-soluble ratiometric TPEF chemosensor EIN that is specifically responsive and singularly sensitive to mitochondria viscosity in living cells. Because its fluorescence emission bands at two different wavelengths show obvious enhancement with increased solvent viscosity, we found that the fluorescence intensity ratio (I569/I384) versus the logarithm of the viscosity (logη) enables monitoring and quantifying of abnormal changes of mitochondria viscosity. More importantly, EIN was successfully utilized to distinguish the normal and nystatin treated HepG2 cell viscosity difference of mitochondria. In a word, the merits of the NIR property, high selectivity and signal ratio provide a more convenient means for studying biological processes and mitochondria viscosity related diseases.
Co-reporter:Jingyun Tan, Yujin Zhang, Meirong Zhang, Xiaohe Tian, Yiming Wang, Shengli Li, Chuankui Wang, Hongping Zhou, Jiaxiang Yang, Yupeng Tian and Jieying Wu
Journal of Materials Chemistry A 2016 - vol. 4(Issue 15) pp:NaN3267-3267
Publication Date(Web):2016/03/04
DOI:10.1039/C6TC00382F
Designing small molecules with large two-photon absorption cross sections is urgently needed. In the present work, six novel chalcone thiophene derivatives were obtained by tuning the terminal electron-withdrawing/donating groups rationally. Their structure–property relationship was investigated both experimentally and theoretically. Crystallographic studies revealed that structural diversity was mainly influenced by ethyloxy groups. Both the alternation of electron-withdrawing/donating groups and the polarity of different solvents had a considerable influence on their photophysical properties. The results of UV-vis and one-/two-photon excited emission spectra showed that the high polarity solvents increased the quantum yields (Φ) and two-photon absorption cross-sections (σ) of type C chalcones, while they decreased those of type OC chalcones. It should be highlighted that as they are small molecules, favorable Φ and σ values were obtained. Finally, a preliminary attempt has been made in the biological imaging field, with satisfactory results that C-1 and OC-1 could locate uniformly in a cytosolic membrane-like system.
![Pyridinium, 1,1',1''-[(2,4,6-trimethyl-1,3,5-benzenetriyl)tris(methylene)]tris[4-carboxy-, bromide (1:3)](/data/chemimg/3718700/1246090-62-9.png)
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![Ethanol, 2-[methyl[4-(2-nitroethenyl)phenyl]amino]-](http://img.cochemist.com/ccimg/606200/606100-51-0_b.png)
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![2-Propenoic acid, 2-cyano-3-[4-(diphenylamino)phenyl]-, (2E)-](http://img.cochemist.com/ccimg/502700/502635-15-6_b.png)
![Benzaldehyde, 3,4,5-tris[2-(2-methoxyethoxy)ethoxy]-](http://img.cochemist.com/ccimg/422300/422267-98-9.png)
![Benzaldehyde, 3,4,5-tris[2-(2-methoxyethoxy)ethoxy]-](http://img.cochemist.com/ccimg/422300/422267-98-9_b.png)
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![Phosphonium, [[4-(dibutylamino)phenyl]methyl]triphenyl-, iodide](http://img.cochemist.com/ccimg/249600/249514-82-7_b.png)
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![Pyridinium,4-[2-[4-(dimethylamino)phenyl]ethenyl]-1-(3-sulfopropyl)-, inner salt](http://img.cochemist.com/ccimg/131100/131032-72-9_b.png)
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![Phosphonic acid, P-[[4-(diphenylamino)phenyl]methyl]-, diethyl ester](/data/chemimg/104500/126150-12-7_b.png)
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![Pyridinium, 4-[(1E)-2-[4-(dibutylamino)phenyl]ethenyl]-1-methyl-, iodide](http://img.cochemist.com/ccimg/97900/97807-64-2_b.png)
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![[4-(DIETHYLAMINO)PHENYL]METHANOL](http://img.cochemist.com/ccimg/75000/74974-49-5_b.png)
![6,7,8,9,10,11,17,18-octahydro-5H-dibenzo[e,n][1,4]dioxa[8,12]diazacyclopentadecine](http://img.cochemist.com/ccimg/65700/65639-43-2.png)
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![Benzaldehyde, 4-[ethyl(2-hydroxyethyl)amino]-](http://img.cochemist.com/ccimg/63700/63619-28-3.png)
![Benzaldehyde, 4-[ethyl(2-hydroxyethyl)amino]-](http://img.cochemist.com/ccimg/63700/63619-28-3_b.png)
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![Poly[(8-amino-1,3,4,6,7,9,9b-heptaazaphenalene-2,5-diyl)imino]](http://img.cochemist.com/ccimg/32600/32518-77-7.png)
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![Anthracene, 9-[2-(4-nitrophenyl)ethenyl]-](http://img.cochemist.com/ccimg/22300/22271-30-3.png)
![Anthracene, 9-[2-(4-nitrophenyl)ethenyl]-](http://img.cochemist.com/ccimg/22300/22271-30-3_b.png)
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![[(sulfonatoperoxy)sulfonyl]oxidanide](http://img.cochemist.com/ccimg/15100/15092-81-6.png)
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