Co-reporter:Jinfang Zhang;Linpei Gong;Jiaoyang Feng;Junjie Wu
New Journal of Chemistry (1998-Present) 2017 vol. 41(Issue 16) pp:8107-8117
Publication Date(Web):2017/08/07
DOI:10.1039/C7NJ01072A
Herein, two new Zn(II)/Cd(II) MOFs, namely {[Zn2(1,4-ndc)2(3-abpt)]·2DMF}n (1) and {[Cd(1,4-ndc)(3-abit)]·H2O}n (2) (1,4-ndc = 1,4-naphthalenedicarboxylic acid, 3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole, 3-abit = 4-amino-3,5-bis(imidazol-1-ylmethyl)-1,2,4-triazole), based on 3-abpt and 3-abit, respectively, containing the same functional group 4-amino-1,2,4-triazole were synthesized and structurally characterized by single crystal and powder X-ray diffractions, elemental analysis, FT-IR spectroscopy, and TGA. X-ray structural analysis reveals that 1 adopts a 2-D 4-connected net with a Schläfli symbol of (44·62) constructed by flywheel-shaped [Zn2(COO)4] dimeric units, 1,4-ndc single bridges, and double bridges composed of 3-abpt and 1,4-ndc. 2 displays a 3-D 2-fold interpenetrated six-connected architecture with a Schläfli symbol of (412·63), fabricated by planar [Cd2(COO)4] dimeric units, 3-abit double bridges, and 1,4-ndc single bridges. 1 and 2 exhibit stronger luminescence as compared to their organic ligands and very rare multifunctional sensing properties. They can selectively and sensitively sense Fe3+ and Al3+ through luminescence quenching and enhancing effect, respectively. Moreover, 1 and 2 show high sensitivity for the detection of TNP than for other nitro aromatics. The mechanisms of 1 and 2 as multifunctional sensors have been preliminarily studied.
Co-reporter:Jinfang Zhang;Linpei Gong;Jiaoyang Feng;Junjie Wu
New Journal of Chemistry (1998-Present) 2017 vol. 41(Issue 16) pp:8107-8117
Publication Date(Web):2017/08/07
DOI:10.1039/C7NJ01072A
Herein, two new Zn(II)/Cd(II) MOFs, namely {[Zn2(1,4-ndc)2(3-abpt)]·2DMF}n (1) and {[Cd(1,4-ndc)(3-abit)]·H2O}n (2) (1,4-ndc = 1,4-naphthalenedicarboxylic acid, 3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole, 3-abit = 4-amino-3,5-bis(imidazol-1-ylmethyl)-1,2,4-triazole), based on 3-abpt and 3-abit, respectively, containing the same functional group 4-amino-1,2,4-triazole were synthesized and structurally characterized by single crystal and powder X-ray diffractions, elemental analysis, FT-IR spectroscopy, and TGA. X-ray structural analysis reveals that 1 adopts a 2-D 4-connected net with a Schläfli symbol of (44·62) constructed by flywheel-shaped [Zn2(COO)4] dimeric units, 1,4-ndc single bridges, and double bridges composed of 3-abpt and 1,4-ndc. 2 displays a 3-D 2-fold interpenetrated six-connected architecture with a Schläfli symbol of (412·63), fabricated by planar [Cd2(COO)4] dimeric units, 3-abit double bridges, and 1,4-ndc single bridges. 1 and 2 exhibit stronger luminescence as compared to their organic ligands and very rare multifunctional sensing properties. They can selectively and sensitively sense Fe3+ and Al3+ through luminescence quenching and enhancing effect, respectively. Moreover, 1 and 2 show high sensitivity for the detection of TNP than for other nitro aromatics. The mechanisms of 1 and 2 as multifunctional sensors have been preliminarily studied.
Co-reporter:Kaibin Chu, Yu-Hua Zhou, Jun-Ling Song, Chi Zhang
Polyhedron 2017 Volume 131(Volume 131) pp:
Publication Date(Web):27 July 2017
DOI:10.1016/j.poly.2017.04.015
ABX3 organic–inorganic hybrid perovskite materials, particularly CH3NH3PbI3, have been widely investigated in recent years. However, organic–inorganic hybrid perovskite materials containing N-heterocyclic are still rarely reported. Herein, we discover a new material, namely, (C5N2H9)CdCl3 (1) by slow evaporation method. The structure of compound 1 was determinated by single crystal X-ray diffraction patterns, and it exhibits 1D chain based edge-sharing CdCl5 tetragonal pyramid. FT-IR and powder X-ray diffraction patterns (PXRD) were performed to confirm the purity of the prepared crystals. The optical diffuse-reflectance spectra indicate that (C5N2H9)CdCl3 is a wide band-gap semiconductor with optical band gap of 3.50 eV. Thermogravimetric analysis (TGA) indicates that 1 is thermally stable up to around 226 °C. In addition, based on the measurement of luminescence properties of 1 at room temperature, the emission spectra of 1 shows a blue fluorescent emission peak at 420 nm (λex = 315 nm). And the fluorescence quenching of 1 by acetonitrile has been studied at room temperature.A new ABX3 organic–inorganic hybrid perovskite material, namely, (C5N2H9)CdCl3 (1) has been synthesized by slow evaporation method. The crystal structure of 1 exhibits one dimensional chain-like structure constructing from edge-sharing CdCl5 tetragonal pyramid. It has a blue fluorescent emission peak at 420 nm (λex = 315 nm), the fluorescence quenching effect of 1 by acetonitrile indicates that it may be used as a sensor of acetonitrile.Download high-res image (62KB)Download full-size image
Co-reporter:Xiaojie Wang, Qian Wu, Kaili Jiang, Chuanxi Wang, Chi Zhang
Sensors and Actuators B: Chemical 2017 Volume 252(Volume 252) pp:
Publication Date(Web):1 November 2017
DOI:10.1016/j.snb.2017.05.177
•The MoS2 QDs with high quantum yield is synthesized through one-step hydrothermal route.•As-prepared MoS2 QDs show small size, high stability and good dispersion in aqueous solution.•MoS2 QDs-based nano-sensor is designed for sensitive and selective label-free detection of glucose.Transition metal chalcogenides, especially molybdenum disulfide, have recently got wide attention from researchers because of their unique intrinsic characteristics. However, until now, few literatures have reported the photoluminescent MoS2 materials and their applications. In this work, we reported a bottom-up strategy to synthesize water-soluble molybdenum disulfide quantum dots (MoS2 QDs) through a facile hydrothermal route using sodium molybdate and glutathione as Mo and S sources. The obtained MoS2 QDs show blue emission with a high quantum yield (∼10.3%) and robust dispersibility and storage stability optical property in aqueous solution. During the experiment, we found that in the presence of hydrogen peroxide (H2O2), the fluorescence of MoS2 QDs is quenched due to the interaction between H2O2 and MoS2 QDs. Simultaneously, glucose oxidase catalyzes the oxidation of glucose to produce gluconic acid and H2O2, so we can use this probe to detect glucose. By reason of the high zymolyte specificity of glucose oxidase, the detection of glucose has good selectivity and sensitivity with a detection limit of 5.16 μM. Finally, the method is successfully applied for detection of glucose in fetal bovine serum samples.Download high-res image (108KB)Download full-size image
Co-reporter:Jinfang Zhang, Ding Jia, Mark G. Humphrey, Suci Meng, Michael J. Zaworotko, Marie P. Cifuentes and Chi Zhang
Chemical Communications 2016 vol. 52(Issue 19) pp:3797-3800
Publication Date(Web):28 Jan 2016
DOI:10.1039/C5CC10076C
An ammonium–crown ether host–guest supramolecular cation-templated synthetic methodology has been developed to construct a structurally unprecedented heterobicluster–metal coordination polymer (HCM-CP 1) based on tetranuclear clusters [WS4Cu3]+ with different connection environments, pentanuclear clusters [WS4Cu4]2+, and Cu+ building metal ions. HCM-CP 1 exhibits enhanced NLO properties, which may be ascribed to the incorporation of diverse building cluster components.
Co-reporter:Aijian Wang, Yun Wang, Wang Yu, Zhipeng Huang, Yu Fang, Lingliang Long, Yinglin Song, Marie P. Cifuentes, Mark G. Humphrey, Long Zhang, Jianda Shao and Chi Zhang
RSC Advances 2016 vol. 6(Issue 24) pp:20120-20127
Publication Date(Web):29 Jan 2016
DOI:10.1039/C5RA26677G
Multi-walled carbon nanotube (MWCNT)/TiO2 nanocomposites have been prepared by a hydrothermal method and characterized by Fourier-transform infrared, Raman, and X-ray photoelectron spectroscopies, X-ray powder diffraction, and transmission electron microscopy. Their viability as nonlinear optical (NLO) materials has been examined using the Z-scan technique at 532 nm with both nanosecond and picosecond laser pulses, the NLO and optical limiting (OL) performance being found to be dependent on the TiO2 content. At the wavelength used, an enhanced OL response was observed for the M1.00 nanocomposite and ascribed to a combination of mechanisms.
Co-reporter:Jinfang Zhang, Yuhang Liu, Linpei Gong, Chi Zhang
Polyhedron 2016 Volume 107() pp:68-77
Publication Date(Web):9 March 2016
DOI:10.1016/j.poly.2016.01.013
The pseudohalogen ligands affecting the architectures of heterothiometallic Mo(W)/S/Cu(Ag) cluster-based coordination polymers (CPs) was firstly explored. In the presence of CuCN or CuSCN with distinct pseudohalogen ligands, two unique W/S/Cu cluster-based CPs [WS4Cu3(CN)(4,4′-bipy)2]n (1, 4,4′-bipy = 4,4′-bipyridine) and {[WS4Cu4(4,4′-bipy)4][WS4Cu4(SCN)4(4,4′-bipy)2]·0.5DMSO}n (2) were achieved by interdiffusion reaction of (NH4)2WS4 and 4,4′-bipy. 1 and 2 were characterized by X-ray single and powder crystal diffractions, elemental analysis, IR, UV–Vis, thermogravimetric analysis. 1 exhibits a neutral 2-D (4,4) network, fabricated by 4-connected T-shaped [WS4Cu3]+ clusters, single CN− bridges and double 4,4′-bipy bridges. While, 2 possesses an unusual 3-D fourfold non-equivalent interpenetrated architecture, consisting of two cationic and two anionic planar ‘open’ [WS4Cu4]2+ cluster-based frameworks; the cationic and anionic architectures are constructed by double 4,4′-bipy bridges and single 4,4′-bipy bridges, respectively, and all show the diamondoid topologies.The pseudohalogen ligands affecting the architectures of Mo(W)/S/Cu(Ag) cluster-based coordination polymers (CPs) was firstly explored, which results in a 2-D T-shaped [WS4Cu3]+ cluster-based (4,4) network and a 3-D planar ‘open’ [WS4Cu4]2+ cluster-based CP with very scarce non-equivalent cationic and anionic interpenetrated framework.
Co-reporter:Aijian Wang;Jingbao Song;Zhipeng Huang;Yinglin Song;Wang Yu
Nano Research 2016 Volume 9( Issue 2) pp:458-472
Publication Date(Web):2016 February
DOI:10.1007/s12274-015-0928-2
Co-reporter:Jinfang Zhang, Yuhang Liu, Linpei Gong, Guozhi Xu, Chi Zhang
Polyhedron 2016 Volume 109() pp:67-74
Publication Date(Web):18 April 2016
DOI:10.1016/j.poly.2016.01.040
The solvent-coordinated metal cations as templates affecting the architectures of anionic heterothiometallic Mo(W)/S/Ag polymeric clusters was investigated. Four W/S/Ag polymeric clusters {[Tb(DMSO)8][W3S12Ag3]}n (1, DMSO = dimethyl sulfoxide), {[Tb(DMF)8][W3S12Ag3]}n (2, DMF = N,N′-dimethylformamide), {[Tb(NMP)8][W4S16Ag5]}n (3, NMP = N-methyl-2-pyrrolidone) and {[Mg(NMP)6][W2S8Ag2]·2NMP}n (4) with distinct 1-D anionic structures were obtained by the reactions of (NH4)2WS4, AgI and M(NO3)x (M = Tb, x = 3; M = Mg, x = 2) in corresponding solvents (DMSO, DMF or NMP). 1–4 were determined by elemental analysis, IR, UV–Vis, thermogravimetric analysis, X-ray powder and single crystal diffractions. Directed by different solvent-coordinated trivalent terbium metal cations, 1 shows a 1-D anionic helical chain architecture; 2 exhibits a 1-D anionic zigzag chain with hexanuclear [W3S12Ag3]3− repeated units; 3 possesses another kind of 1-D anionic zigzag chain with the unique nonanuclear planar square-like [W4S16Ag5]3− repeated units. While induced by NMP-coordinated bivalent magnesium metal cation, 4 exhibits a 1-D anionic linear chain structure.The types of coordinated solvents and the valences of central metals in the cationic templates were shown to have the pronounced effects on the skeletons of 1-D anionic W/S/Ag polymeric clusters.
Co-reporter:Chuanxi Wang, Zhenzhu Xu, Hao Cheng, Huihui Lin, Mark G. Humphrey, Chi Zhang
Carbon 2015 Volume 82() pp:87-95
Publication Date(Web):February 2015
DOI:10.1016/j.carbon.2014.10.035
Carbon dots (CDs) as a class of heavy-metal-free fluorescent nanomaterials has drawn increasing attention in recent years due to their high optical absorptivity, chemical stability, biocompatibility, and low toxicity. Herein, we report a facile method to prepare stable CDs by hydrothermal treatment of glucose (glc) in the presence of glutathione (GSH). With this approach, the formation and the surface passivation of CDs are carried out simultaneously, resulting in intrinsic fluorescence emission. The influence of reaction temperature, reaction time and feed ratio of GSH/glc on the photoluminescence property of CDs is studied. The as-prepared CDs are characterized by UV–Vis, photoluminescence, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and transmission electron microscope, from which their structural information and property are interpreted. These CDs may be useful as pH sensors or as versatile nanothermometry devices based on the pronounced temperature dependence of their steady-state fluorescence emission spectra, which changes considerably over the physiological temperature range (15–60 °C).
Co-reporter:Aijian Wang, Wang Yu, Yu Fang, Yinglin Song, Ding Jia, Lingliang Long, Marie P. Cifuentes, Mark G. Humphrey, Chi Zhang
Carbon 2015 Volume 89() pp:130-141
Publication Date(Web):August 2015
DOI:10.1016/j.carbon.2015.03.037
TiO2/reduced graphene oxide (RGO) nanocomposites Gx (RGO titania nanocomposite, x grams tetrabutyl titanate per 0.03 g RGO, x = 0.25, 0.50, 1.00) were prepared by a hydrothermal method: graphene oxide was reduced to RGO in a 2:1 water:ethanol mixture in the presence of varying quantities of tetrabutyl titanate, which deposited as TiO2 on the RGO sheets. The nanocomposites were characterized by a combination of Fourier transform infrared spectroscopy, diffuse reflectance ultraviolet–visible spectroscopy, photoluminescence spectroscopy, Raman spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy studies. The nanocomposite G0.25 exhibits enhanced nonlinear optical properties compared to its individual components, which is ascribed to a combination of mechanisms. The role of defects and electron/energy transfer in the optical limiting performance of G0.25 was clarified with the help of Raman and photoluminescence spectroscopies. Intensity-dependent switching between reverse saturable absorption and saturable absorption behavior was observed with the G0.50 nanocomposite.
Co-reporter:Chuanxi Wang, Hao Cheng, Yijun Huang, Zhenzhu Xu, Huihui Lin and Chi Zhang
Analyst 2015 vol. 140(Issue 16) pp:5634-5639
Publication Date(Web):19 Jun 2015
DOI:10.1039/C5AN00741K
A one-pot sonochemical reaction of Cu(NO3)2 with glutathione (GSH), the latter functioning as a reducing agent and a stabilizing agent, rapidly affords Cu nanoclusters (NCs). The as-prepared GSH–CuNCs possess a small size (∼2.2 ± 0.2 nm), red luminescence with quantum yield (5.3%), and water-dispersibility. Moreover, the fluorescence of the as-prepared GSH–CuNCs is responsive to pH so that the intensity of fluorescence increases rapidly with decreasing pH from 9 to 4. Besides, the GSH–CuNCs would be aggregated by Pb2+ ions in aqueous solution which results in quenching of the fluorescence. Therefore, such GSH–CuNCs would be excellent candidates as fluorescent probes for the label-free detection of Pb2+ with the limit of detection at 1.0 nM. Importantly, CAL-27 cells are used as models to achieve potential application as probes for monitoring Pb2+ in living cells. Thus, these fluorescent CuNCs could work as an alternative to conventional fluorescent probes for biolabeling, sensing and other applications.
Co-reporter:Chuanxi Wang, Yijun Huang, Huihui Lin, Zhenzhu Xu, Jiapeng Wu, Mark G. Humphrey and Chi Zhang
RSC Advances 2015 vol. 5(Issue 76) pp:61586-61592
Publication Date(Web):13 Jul 2015
DOI:10.1039/C5RA13475G
In this work, we develop a novel dual-emitting hollow TiO2 microsphere with high stability and attractive thermal sensitivity, which could work as nanosensor for accurately measuring temperature. This nanosensor is prepared through coating gold nanocluster (AuNCs) on the surface of carbon dots-doped hollow TiO2 microsphere. As-prepared nanosensor shows characteristic dual-emitting property of carbon dots (CDs, blue fluorescence) and AuNCs (red fluorescence) under a single excitation wavelength. Moreover, upon increasing the temperature, the intensity of red emission from the AuNCs continuously quenched, whereas that of blue emission from the CDs remained nearly constant. The different response results in a continuous fluorescence color change from red to purple that can be clearly observed by the naked eyes. Thus, as-prepared dual-emitting hollow TiO2 microsphere could be used as optical thermometry by taking the advantage of the temperature sensitivity of their fluorescence intensity ratio (red/blue) with high reliability and accuracy, which change considerably over the wide temperature range (20–80 °C) with small temperature resolution (∼0.5 °C). Additionally, this nanosensor is successfully applied in 10 mM buffered saline (PBS) solution with physiological temperature ranging from 20 to 45 °C, which suggests as-prepared dual-emitting microspheres have promising applications in vivo temperature sensing.
Co-reporter:Chuanxi Wang, Huihui Lin, Zhenzhu Xu, Hao Cheng and Chi Zhang
RSC Advances 2015 vol. 5(Issue 20) pp:15621-15626
Publication Date(Web):28 Jan 2015
DOI:10.1039/C4RA15632C
Herein, we report flowerlike MoS2/CdS heterostructures prepared by a simple hydrothermal method. The structure and morphology of products are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The experimental results indicate that the as-prepared products show a flowerlike nanostructure with size at 800 nm. This flowerlike nanostructure has a large surface area and may provide a better anchoring surface for adsorbing molecules. Very importantly, as-prepared flowerlike MoS2/CdS heterostructures exhibit excellent performance in adsorption and a higher photocatalytic activity for degrading methylene blue under the excitation of visible light than pure CdS or pure MoS2. These characteristics enable this novel flowerlike heterostructural nanomaterial to perform potential applications in water treatment, degradation of dye pollutants, and environmental cleaning.
Co-reporter:Huihui Lin, Chuanxi Wang, Jiapeng Wu, Zhenzhu Xu, Yijun Huang and Chi Zhang
New Journal of Chemistry 2015 vol. 39(Issue 11) pp:8492-8497
Publication Date(Web):17 Aug 2015
DOI:10.1039/C5NJ01698C
Although the synthesis of two-dimensional (2D) layered MoS2 nanomaterials has been developing rapidly, there are many technical issues in preparing MoS2 quantum dots (QDs) with photoluminescence properties. Herein, we design a facile colloidal chemical route to prepare photoluminescent MoS2 QDs using ammonium tetrathiomolybdate ((NH4)2MoS4) as a precursor and oleyl amine as a reducing agent. The optical properties and structure of as-prepared MoS2 QDs are investigated systematically. The resultant MoS2 QDs exhibit fluorescence (λmax = 575 nm; quantum yield, 4.4%), spherical morphology with a uniform thickness of ∼3 nm and an excitation-dependent PL phenomenon. Moreover, the resultant MoS2 QDs show size-dependent tunable photoluminescence in the wide visible region. With the help of amphiphilic compounds, the resultant MoS2 QDs could be transferred from an organic to an aqueous phase. MoS2 QDs in aqueous solution have many advantages, such as good dispersion, low toxicity and photoluminescent properties, which make them promising materials for application in optoelectronic and biological fields. In this study, the 293T cells are used as a model to evaluate the fluorescence imaging of MoS2 QDs. The results confirm that the fluorescent signal appears in the cytoplasm which demonstrates that as-prepared MoS2 QDs could be used as a probe for real-time optical cellular imaging.
Co-reporter:Jinfang Zhang, Weitao Chen, Yu Fang, Ding Jia, Yinlin Wang, Yinglin Song, Chi Zhang
Polyhedron 2015 Volume 101() pp:1-5
Publication Date(Web):24 November 2015
DOI:10.1016/j.poly.2015.07.044
Directed by potassium–crownether host–guest cation, a unique octameric eicosanuclear heterothiometallic Mo/S/Cu cluster [K(dibenzo-18-crown-6)(DMF)2]4[Mo8S32Cu12] (1) was synthesized by the reaction of (NH4)2MoS4, CuI, KI, dibenzo-18-crown-6 in DMF solution. 1 was characterized by elemental analysis, IR, thermogravimetric analysis, X-ray powder and single crystal diffractions. 1 crystallizes in the tetragonal space group I41cd. The anionic octameric eicosanuclear [Mo8S32Cu12]4− cluster exhibits a supra-cubane-like skeleton, fabricated by four nest-shaped clusters [Mo(μ1-S)(μ3-S)3Cu3]+ and four flywheel-shaped clusters [Mo(μ2-S)3(μ4-S)Cu3]+ linking together through shared Cu atoms. The cation [K(dibenzo-18-crown-6)(DMF)2]+ of 1 exhibits the host–guest configuration, where K+ is embedded in the center of dibenzo-18-crown-6. Furthermore, Z-scan studies (532 nm, 21 ps pulses) reveal that 1 possesses effective third-order nonlinear optical (NLO) properties.A unique anionic octameric supra-cubane-like heterothiometallic Mo/S/Cu cluster was synthesized in the presence of potassium–crownether host–guest cation. Furthermore, Z-scan studies reveal that this cluster possesses effective third-order nonlinear optical properties.
Co-reporter:Jinfang Zhang, Chao Wang, Chi Zhang
Polyhedron 2015 Volume 92() pp:93-98
Publication Date(Web):28 May 2015
DOI:10.1016/j.poly.2015.03.018
In the presence of chelated ligand 1,10-Phenanthroline (phen), two heterothiometallic W/S/Cu dimeric clusters {[WS4Cu4Br2(phen)2]2·MeCN}2 (1) and {[CuBr(phen)2]2[WOS3Cu3Br2(phen)]2} (2) were obtained by the reactions of CuBr and (NH4)2WS4 or (NH4)2WOS3 in DMF solutions. 1 and 2 were determined by elemental analyses, IR, UV–Vis, X-ray powder and single crystal diffraction. 1 is constructed by two parallel neutral pentanuclear planar ‘open’ [WS4Cu4Br2(phen)2] clusters bridging together through two μ2-Br bridges to form a rare dimeric architecture. 2 contains two [CuBr(phen)2]+ cations and one dimeric {[WOS3Cu3Br2(phen)]2}2− anion, constructed by two tetranuclear nest-shaped [WOS3Cu3]+ clusters linking together via a pair of μ2-Br bridges. Furthermore, the photocatalytic activities of heterothiometallic clusters were firstly investigated under visible light irradiation by monitoring the photodegradation of methylene blue (MB), which shows 1 and 2 exhibit effective photocatalytic performances.Graphical abstractTwo unique W/S/Cu dimeric clusters were constructed by pentanuclear planar ‘open’ and tetranuclear nest-shaped building clusters, respectively. Furthermore, the photocatalytic activities of heterothiometallic clusters were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible light irradiation.
Co-reporter:Dr. Jianghua Li;Ding Jia;Dr. Suci Meng;Dr. Jinfang Zhang;Dr. Marie P. Cifuentes;Dr. Mark G. Humphrey;Dr. Chi Zhang
Chemistry - A European Journal 2015 Volume 21( Issue 21) pp:7914-7926
Publication Date(Web):
DOI:10.1002/chem.201404803
Abstract
Three unusual three-dimensional (3D) tetrazine chromophore-based metal–organic frameworks (MOFs) {(Et4N)[WS4Cu3(CN)2(4,4′-pytz)0.5]}n (1), {[MoS4Cu4(CN)2(4,4′-pytz)2]⋅CH2Cl2}n (2), and {[WS4Cu3(4,4′-pytz)3]⋅[N(CN)2]}n (3; 4,4′-pytz=3,6-bis(4-pyridyl)tetrazine) have been synthesized and characterized by using FTIR and UV/Vis spectroscopy, elemental analysis, powder X-ray diffraction, gel permeation chromatography, steady-state fluorescence, and thermogravimetric analysis; their identities were confirmed by single-crystal X-ray diffraction studies. MOF 1 possesses the first five-connected M/S/Cu (M=Mo, W) framework with an unusual 3D (44⋅66) topology constructed from T-shaped [WS4Cu3]+ clusters as nodes and single CN−/4,4′-pytz bridges as linkers. MOF 2 features a novel 3D MOF structure with (420⋅68) topology, in which the bridging 4,4′-pytz ligands exhibit unique distorted arch structures. MOF 3 displays the first 3D MOF structure based on flywheel-shaped [WS4Cu3]+ clusters with a non-interpenetrating honeycomb-like framework and a heavily distorted “ACS” topology. Steady-state fluorescence studies of 1–3 reveal significant fluorescence emissions. The nonlinear optical (NLO) properties of 1–3 were investigated by using a Z-scan technique with 5 ns pulses at λ=532 nm. The Z-scan experimental results show that the π-delocalizable tetrazine-based 4,4′-pytz ligands contribute to the strong third-order NLO properties exhibited by 1–3. Time-dependent density functional theory studies afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.
Co-reporter:Aijian Wang;Wang Yu;Zhengguo Xiao;Yinglin Song;Lingliang Long
Nano Research 2015 Volume 8( Issue 3) pp:870-886
Publication Date(Web):2015 March
DOI:10.1007/s12274-014-0569-x
Reduced graphene oxide (RGO) has been covalently functionalized with porphyrin moieties by two methods: A straightforward Prato reaction (i.e. a 1,3-dipolar cycloaddition) with sarcosine and a formyl-containing porphyrin, and a stepwise method that involves a 1,3-dipolar cycloaddition to the RGO surface using 4-hydroxybenzaldehyde, followed by nucleophilic substitution with an appropriate porphyrin. The chemical bonding of porphyrins to the RGO surface has been confirmed by ultraviolet/visible absorption, fluorescence, Fourier-transform infrared, and Raman spectroscopies, X-ray powder diffraction and X-ray photoelectron spectroscopy, transmission electron and atomic force microscopy, and thermogravimetric analysis; this chemical attachment assures efficient electron/energy transfer between RGO and the porphyrin, and affords improved optical nonlinearities compared to those of the RGO precursor and the pristine porphyrin.
Co-reporter:Jinfang Zhang;Chao Wang;Weitao Chen;Huihui Lin
Transition Metal Chemistry 2015 Volume 40( Issue 4) pp:405-412
Publication Date(Web):2015 May
DOI:10.1007/s11243-015-9930-5
Reactions of (NH4)WS4, CuCN and pyridine (Py) in different reaction solvents, namely DMF, DMSO and aniline, generated three isomeric heterothiometallic W/S/Cu cluster-based coordination polymers [WS4Cu4(CN)2(Py)4]n (1 and 2) and {[WS4Cu4(CN)2(Py)4]2·4CH3CN}n3. All three complexes are constructed from planar ‘open’ [W(µ3-S)4Cu4]2+ clusters, CN− bridges and terminal Py ligands, but exhibit distinct architectures, consisting of a unique 1-D serrated chain for 1, a 2-D (4,4) network for 2 and a 1-D linear chain for 3. The photocatalytic activities of complex 1 were explored by monitoring the photodegradation of methylene blue, revealing that this complex exhibits effective photocatalytic properties under visible light irradiation.
Co-reporter:Chan Wang, Chuanxi Wang, Lin Xu, Hao Cheng, Quan Lin and Chi Zhang
Nanoscale 2014 vol. 6(Issue 3) pp:1775-1781
Publication Date(Web):20 Nov 2013
DOI:10.1039/C3NR04835G
The development of functional copper nanoclusters (Cu NCs) is becoming increasingly widespread in consumer technologies due to their applications in cellular imaging and catalysis. Herein, we report a simple protein-directed synthesis of stable, water-soluble and fluorescent Cu NCs, using BSA as the stabilising agent. Meanwhile, in this study, hydrazine hydrate (N2H4·2H2O) was used as the reducing agent. N2H4·2H2O was a mild reducing agent suggesting that all processes could be operated at room temperature. The as-prepared Cu NCs showed red fluorescence with a peaking center at 620 nm (quantum yield 4.1%). The fluorescence of the as-prepared BSA–Cu NCs was responsive to pH in that the intensity of fluorescence increased rapidly by decreasing the pH from 12 to 6. Besides, with an arresting set of features including water-dispersibility, red fluorescence, good biocompatibility, surface-bioactivity and small size, the resultant BSA–Cu NCs could be used as probes for cellular imaging and catalysis. In this study, CAL-27 cells and the reaction of oxidation of styrene are used as models to achieve fluorescence imaging and elucidate the catalytic activity of the as-prepared BSA–Cu NCs.
Co-reporter:Aijian Wang, Lingliang Long, Suci Meng, Xiufen Li, Wei Zhao, Yinglin Song, Marie P. Cifuentes, Mark G. Humphrey and Chi Zhang
Organic & Biomolecular Chemistry 2013 vol. 11(Issue 25) pp:4250-4257
Publication Date(Web):16 Apr 2013
DOI:10.1039/C3OB40323H
A novel porphyrin derivative bearing one D–π–A–π–D pyrimidine chromophore at the periphery was designed, prepared, and studied using the Z-scan technique, the results showing that this compound exhibits enhanced nonlinear optical (NLO) absorption, refraction and optical limiting responses. The significant NLO properties can be ascribed to an effective combination of distinct nonlinear mechanisms.
Co-reporter:Dr. Aijian Wang;Yu Fang;Dr. Lingliang Long;Dr. Yinglin Song;Wang Yu;Wei Zhao;Dr. Marie P. Cifuentes;Dr. Mark G. Humphrey;Dr. Chi Zhang
Chemistry - A European Journal 2013 Volume 19( Issue 42) pp:
Publication Date(Web):
DOI:10.1002/chem.201390164
Co-reporter:Dr. Aijian Wang;Yu Fang;Dr. Lingliang Long;Dr. Yinglin Song;Wang Yu;Wei Zhao;Dr. Marie P. Cifuentes;Dr. Mark G. Humphrey;Dr. Chi Zhang
Chemistry - A European Journal 2013 Volume 19( Issue 42) pp:14159-14170
Publication Date(Web):
DOI:10.1002/chem.201302477
Abstract
Two multi-walled carbon nanotube (MWCNT)-based nanohybrids, MWCNT–ZnTPP and MWCNT–TPP (TPP=5-[4-{2-(4-formylphenoxy)- ethyloxy}phenyl]-10,15,20-triphenylporphyrin, ZnTPP=5-[4-{(4-formylphenyl)ethynyl}phenyl]-10,15,20-triphenylporphinatozinc(II)), were prepared directly from pristine MWCNTs through 1,3-dipolar cycloaddition reactions. Covalent attachment of the porphyrins to the surfaces of the MWCNTs was confirmed by Fourier transform infrared spectroscopy, ultraviolet/visible absorption, fluorescence, Raman, and X-ray photoelectron spectroscopy, elemental analysis, transmission electron microscopy, and thermogravimetric analysis. Attachment of the porphyrin moieties to the surface of the MWCNTs significantly improves the solubility and ease of processing of these MWCNT–porphyrin composite materials. Z-scan studies reveal that these MWCNT–porphyrin nanohybrids exhibit enhanced nonlinear optical properties under both nanosecond and picosecond laser pulses at λ=532 nm in comparison with free MWCNTs and the free porphyrin chromophores, whereas superior optical limiting performance was displayed by MWCNT–porphyrin composite materials rather than MWCNTs/ZnTPP and MWCNTs/TPP blends, which is consistent with a remarkable accumulation effect as a result of the covalent linkage between the porphyrin and the MWCNTs.
Co-reporter:Jinfang Zhang, Linpei Gong, YinLin Wang, Junjie Wu, Jiaoyang Feng, Chi Zhang
Polyhedron (17 February 2017) Volume 123() pp:
Publication Date(Web):17 February 2017
DOI:10.1016/j.poly.2016.10.030
The study on the auxiliary ligands affecting the architectures of 2,6-bip-bridged coordination polymers (CPs) is demonstrated [2,6-bip = 2,6-bis(imidazol-1-yl)pyridine]. Two distinct Cd-2,6-bip CPs [Cd(2,6-bip)2(NCS)2]n (1) and {Cd(2,6-bip)[N(CN)2]2}n (2) were constructed in the presence of the auxiliary ligands thiocyanate SCN− and dicyanamide N(CN)2−, respectively. 1–2 were determined by FT-IR, elemental analyses, powder and single crystal X-ray diffractions. 1 exhibits a two-dimensional (2-D) layer structure, only sustained by 2,6-bip single bridges; while 2 has a distinct 2-D layer architecture, supported by 2,6-bip and N(CN)2− double bridges and N(CN)2− single bridges. The luminescence and nitrobenzene sensing properties of 1–2 were investigated, which reveals that 1–2 exhibit significantly stronger luminescence emissions than that of free 2,6-bip organic ligand, and the most sensitive for nitrobenzene detection.The auxiliary ligands affecting the configurations of 2,6-bip-bridged coordination polymers (CPs) was explored, which results in two distinct 2-D CPs 1 and 2. Furthermore, 1 and 2 exhibit significantly stronger luminescence emissions than that of free 2,6-bip organic ligand, and the most sensitive for nitrobenzene detection.
Co-reporter:Chuanxi Wang, Kaili Jiang, Zhenzhu Xu, Huihui Lin and Chi Zhang
Inorganic Chemistry Frontiers 2016 - vol. 3(Issue 4) pp:NaN522-522
Publication Date(Web):2016/01/13
DOI:10.1039/C5QI00273G
In this paper, a novel “turn-on” chemosensor for detecting temperature and Fe3+ has been designed. This nanosensor is based on the aggregation-induced emission enhancement (AIEE) properties of fluorescent carbon dots (CDs). The CDs prepared by a facile hydrothermal route show blue emission (λem = 505 nm) with a quantum yield of 4.7%. The resultant CDs are modified by glutathione (GSH) on the surface through the carbodiimide-activated coupling reaction. The as-prepared GSH-CDs show good dispersion, high fluorescence and AIEE phenomenon. Resultant GSH-CDs would be aggregated by Fe3+ ions in aqueous solution which results in enhanced fluorescence. Therefore, such GSH-CDs would be excellent candidates as fluorescent probes for the label-free detection of Fe3+ ions with a limit of detection of 0.1 μM. Moreover, the PL intensity of GSH-CDs increases progressively with increasing temperature and they could be used in optical thermometry over a wide temperature range (25–80 °C) with small temperature resolution (∼0.5 °C). Using MC3T3-E1 cells as the model, the resultant nanosensor is demonstrated to monitor temperature and Fe3+ ions in cells. Thus, resultant GSH-CDs could be used as a “turn-on” sensor for highly sensitive and selective detection of temperature and Fe3+ ions in aqueous solution and biosystems.
Co-reporter:Aijian Wang, Lingliang Long, Suci Meng, Xiufen Li, Wei Zhao, Yinglin Song, Marie P. Cifuentes, Mark G. Humphrey and Chi Zhang
Organic & Biomolecular Chemistry 2013 - vol. 11(Issue 25) pp:NaN4257-4257
Publication Date(Web):2013/04/16
DOI:10.1039/C3OB40323H
A novel porphyrin derivative bearing one D–π–A–π–D pyrimidine chromophore at the periphery was designed, prepared, and studied using the Z-scan technique, the results showing that this compound exhibits enhanced nonlinear optical (NLO) absorption, refraction and optical limiting responses. The significant NLO properties can be ascribed to an effective combination of distinct nonlinear mechanisms.
Co-reporter:Jinfang Zhang, Ding Jia, Mark G. Humphrey, Suci Meng, Michael J. Zaworotko, Marie P. Cifuentes and Chi Zhang
Chemical Communications 2016 - vol. 52(Issue 19) pp:NaN3800-3800
Publication Date(Web):2016/01/28
DOI:10.1039/C5CC10076C
An ammonium–crown ether host–guest supramolecular cation-templated synthetic methodology has been developed to construct a structurally unprecedented heterobicluster–metal coordination polymer (HCM-CP 1) based on tetranuclear clusters [WS4Cu3]+ with different connection environments, pentanuclear clusters [WS4Cu4]2+, and Cu+ building metal ions. HCM-CP 1 exhibits enhanced NLO properties, which may be ascribed to the incorporation of diverse building cluster components.
![Benzene, 1-bromo-4-[(1E)-2-[4-(1,1-dimethylethyl)phenyl]ethenyl]-](http://img.cochemist.com/ccimg/660500/660437-82-1.png)
![Benzene, 1-bromo-4-[(1E)-2-[4-(1,1-dimethylethyl)phenyl]ethenyl]-](http://img.cochemist.com/ccimg/660500/660437-82-1_b.png)
![Benzenamine, 4-[[tris(1-methylethyl)silyl]ethynyl]-](http://img.cochemist.com/ccimg/391200/391198-48-4.png)
![Benzenamine, 4-[[tris(1-methylethyl)silyl]ethynyl]-](http://img.cochemist.com/ccimg/391200/391198-48-4_b.png)
![Benzene, 1,3,5-tris[2-(4-ethynylphenyl)ethynyl]-](/data/chemimg/447900/211739-82-1.png)
![Benzene, 1,3,5-tris[2-(4-ethynylphenyl)ethynyl]-](/data/chemimg/447900/211739-82-1_b.png)
![21H,23H-Porphine, 5-[4-(2-bromoethoxy)phenyl]-10,15,20-triphenyl-](/data/chemimg/104200/128175-51-9.png)
![21H,23H-Porphine, 5-[4-(2-bromoethoxy)phenyl]-10,15,20-triphenyl-](/data/chemimg/104200/128175-51-9_b.png)
![Benzenesulfonic acid,4-[2-[4-(dimethylamino)phenyl]diazenyl]-](http://img.cochemist.com/ccimg/600/502-02-3.png)
![Benzenesulfonic acid,4-[2-[4-(dimethylamino)phenyl]diazenyl]-](http://img.cochemist.com/ccimg/600/502-02-3_b.png)
![Benzaldehyde, 4-[2-[4-(10,15,20-triphenyl-21H,23H-porphin-5-yl)phenoxy]ethoxy]-](/data/chemimg/3723800/479670-14-9.png)
![Benzaldehyde, 4-[2-[4-(10,15,20-triphenyl-21H,23H-porphin-5-yl)phenoxy]ethoxy]-](/data/chemimg/3723800/479670-14-9_b.png)
