Co-reporter:Cheng-Xia Chen, Zhang-Wen Wei, Ji-Jun Jiang, Shao-Ping Zheng, Hai-Ping Wang, Qian-Feng Qiu, Chen-Chen Cao, Dieter Fenske, and Cheng-Yong Su
Journal of the American Chemical Society May 3, 2017 Volume 139(Issue 17) pp:6034-6034
Publication Date(Web):April 7, 2017
DOI:10.1021/jacs.7b01320
A robust Zr-MOF (LIFM-28) containing replaceable coordination sites for additional spacer installation has been employed to demonstrate a swing- or multirole strategy for multifunctional MOFs. Through reversible installation/uninstallation of two types of spacers with different lengths and variable functional groups, different tasks can be accomplished using the same parent MOF. An orthogonal optimizing method is applied with seven shorter (L1–7) and six longer (L8–13) spacers to tune the functionalities, achieving multipurpose switches among gas separation, catalysis, click reaction, luminescence, and particularly, ultrahigh methane storage working capacity at 5–80 bar and 298 K.
Co-reporter:Jing-Xiang Zhang;Mei Pan
Journal of Materials Chemistry B 2017 vol. 5(Issue 24) pp:4623-4632
Publication Date(Web):2017/06/22
DOI:10.1039/C7TB00702G
The combination of chemotherapy with photodynamic therapy can lead to improved therapeutic efficiencies and reduced side effects compared to conventional chemotherapy. Chlorambucil (CHL) is a DNA alkylating agent, but problems like drug instability, “off-target” binding and in situ monitoring after administration often limit its clinical application. In this regard, we designed a new heteroleptic Ru(II) complex CHL-RuL, bearing a CHL conjugated pendant, which is desired to serve as an image-guided chemo-photodynamic combined theranostic agent. CHL-RuL shows considerable promise as a photosensitizer for two-photon excitation photodynamic therapy: strong and wide UV-Vis absorption bands centered around 400 nm, strong red emission (∼702 nm) with a long lifetime at the microsecond level, moderate singlet oxygen quantum yield, and significant two-photon absorption cross-section (118 GM). More interestingly, this chemical modification affords CHL-RuL greater cellular uptake and remarkable mitochondria accumulation in HeLa cells. Furthermore, CHL-RuL shows a slight selective cytotoxicity toward carcinoma HeLa cells over normal MRC-5 cells. MTT assay results and two-photon scanning cell imaging demonstrate that CHL-RuL exhibits obvious chemo-photodynamic dual action against HeLa cells.
Co-reporter:Dr. Zhongshu Li;Dr. Xiaodan Chen;Dr. Diego M. Andrada; Dr. Gernot Frenking;Dr. Zoltán Benkö;Yaqi Li;Assoc. Dr. Jeffrey R. Harmer; Dr. Cheng-Yong Su; Dr. Hansjörg Grützmacher
Angewandte Chemie 2017 Volume 129(Issue 21) pp:5838-5843
Publication Date(Web):2017/05/15
DOI:10.1002/ange.201612247
AbstractCarbon phosphides, CnPm, may have highly promising electronic, optical, and mechanical properties, but they are experimentally almost unexplored materials. Phosphaheteroallenes stabilized by N-heterocyclic carbenes undergo a one-electron reduction to yield compounds of the type (L)2C2P2 with diverse structures. The use of imidazolylidenes as ligands L give complexes with a central four-membered ring C2P2, while more electrophilic cyclic diamidocarbenes (DAC) give a compound with an acyclic π-conjugated CP−PC unit. Cyclic C2P2 compounds are best described as non-Kekulé molecules that are stabilized by coordination to the NHC ligands NHC(C2P2)NHC. These species can be easily oxidized to give stable radical cations [(NHC)2C2P2]+.. The remarkably stable molecules with an acylic C2P2 core are best described with electron-sharing bonds (DAC)=C=P−P=C=(DAC).
Co-reporter:Dr. Zhongshu Li;Dr. Xiaodan Chen;Dr. Diego M. Andrada; Dr. Gernot Frenking;Dr. Zoltán Benkö;Yaqi Li;Assoc. Dr. Jeffrey R. Harmer; Dr. Cheng-Yong Su; Dr. Hansjörg Grützmacher
Angewandte Chemie International Edition 2017 Volume 56(Issue 21) pp:5744-5749
Publication Date(Web):2017/05/15
DOI:10.1002/anie.201612247
AbstractCarbon phosphides, CnPm, may have highly promising electronic, optical, and mechanical properties, but they are experimentally almost unexplored materials. Phosphaheteroallenes stabilized by N-heterocyclic carbenes undergo a one-electron reduction to yield compounds of the type (L)2C2P2 with diverse structures. The use of imidazolylidenes as ligands L give complexes with a central four-membered ring C2P2, while more electrophilic cyclic diamidocarbenes (DAC) give a compound with an acyclic π-conjugated CP−PC unit. Cyclic C2P2 compounds are best described as non-Kekulé molecules that are stabilized by coordination to the NHC ligands NHC(C2P2)NHC. These species can be easily oxidized to give stable radical cations [(NHC)2C2P2]+.. The remarkably stable molecules with an acylic C2P2 core are best described with electron-sharing bonds (DAC)=C=P−P=C=(DAC).
Co-reporter: Dr. Mei Pan;Yi-Xuan Zhu;Kai Wu;Ling Chen;Ya-Jun Hou;Shao-Yun Yin;Hai-Ping Wang;Ya-Nan Fan; Dr. Cheng-Yong Su
Angewandte Chemie International Edition 2017 Volume 56(Issue 46) pp:14582-14586
Publication Date(Web):2017/11/13
DOI:10.1002/anie.201708802
AbstractCore–shell or striped heteroatomic lanthanide metal–organic framework hierarchical single crystals were obtained by liquid-phase anisotropic epitaxial growth, maintaining identical periodic organization while simultaneously exhibiting spatially segregated structure. Different types of domain and orientation-controlled multicolor photophysical models are presented, which show either visually distinguishable or visible/near infrared (NIR) emissive colors. This provides a new bottom-up strategy toward the design of hierarchical molecular systems, offering high-throughput and multiplexed luminescence color tunability and readability. The unique capability of combining spectroscopic coding with 3D (three-dimensional) microscale spatial coding is established, providing potential applications in anti-counterfeiting, color barcoding, and other types of integrated and miniaturized optoelectronic materials and devices.
Co-reporter:Yingxia Wang;Hao Cui;Zhang-Wen Wei;Hai-Ping Wang;Li Zhang
Chemical Science (2010-Present) 2017 vol. 8(Issue 1) pp:775-780
Publication Date(Web):2016/12/19
DOI:10.1039/C6SC03288E
An iridium-porphyrin ligand, Ir(TCPP)Cl (TCPP = tetrakis(4-carboxyphenyl)porphyrin), has been utilized to react with HfCl4 to generate a stable Ir(III)-porphyrin metal–organic framework of the formula [(Hf6(μ3-O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3]·solvents (Ir-PMOF-1(Hf)), which possesses two types of open cavities (1.9 × 1.9 × 1.9 and 3.0 × 3.0 × 3.0 nm3) crosslinked through orthogonal channels (1.9 × 1.9 nm2) in three directions. The smaller cavity is surrounded by four catalytic Ir(TCPP)Cl walls to form a confined coordination space as a molecular nanoreactor, while the larger one facilitates reactant/product feeding and release. Therefore, the porous Ir-PMOF-1(Hf) can act as a multi-channel crystalline molecular flask to promote the carbenoid insertion reaction into Si–H bonds, featuring high chemoselectivity towards primary silanes among primary, secondary and tertiary silanes under heterogeneous conditions that are inaccessible by conventional homogeneous catalysts.
Co-reporter:Pei-Yang Su;Li-Bo Huang;Jun-Min Liu;Yi-Fan Chen;Li-Min Xiao;Dai-Bin Kuang;Marcel Mayor
Journal of Materials Chemistry A 2017 vol. 5(Issue 5) pp:1913-1918
Publication Date(Web):2017/01/31
DOI:10.1039/C6TA09314K
The hydrophobic and conductive polymer poly-N-vinylcarbazole (PVK) has been successfully utilized as a multifunctional interlayer between perovskite and the hole transporting material (HTM) for highly stable and efficient perovskite solar cells (PSCs) for the first time. The very thin PVK interlayer can not only protect the perovskite structure from moisture and degradation, but also modulate the interface to reduce charge recombination and promote hole transportation simultaneously. Benefited by coupling this PVK-protection method with the molecular design of an economical and synthetically facile triazatruxene-based HTM (SP-12) featuring good stability, planarity and hole mobility, a reliable power conversion efficiency of 18.8% has been achieved, which is superior to that using the well-studied spiro-OMeTAD (16.9%), demonstrating a promising fabrication approach to efficient and long-term stable PSCs.
Co-reporter:Cheng-Xia Chen;Qian-Feng Qiu;Chen-Chen Cao;Mei Pan;Hai-Ping Wang;Ji-Jun Jiang;Zhang-Wen Wei;Kelong Zhu;Guangqin Li
Chemical Communications 2017 vol. 53(Issue 83) pp:11403-11406
Publication Date(Web):2017/10/17
DOI:10.1039/C7CC06352K
Through stepwise post-synthetic spacer insertion and click reactions, six Zr-MOFs with different types and amounts of functional groups have been constructed based on proto-MOF PCN-700. Their gas adsorption capacities and selectivities have been greatly improved and finely tuned, demonstrating the combinatorial effect of pore surface modification and pore space partition.
Co-reporter:Yi-Fan Chen, Li-Lin Tan, Jun-Min Liu, Su Qin, Zhi-Qiang Xie, Jian-Feng Huang, Yao-Wei Xu, Li-Min Xiao, Cheng-Yong Su
Applied Catalysis B: Environmental 2017 Volume 206(Volume 206) pp:
Publication Date(Web):5 June 2017
DOI:10.1016/j.apcatb.2017.01.040
•Low-cost Calix-3 dyes were firstly applied in photocatalytic H2 production.•Calix-3-sensitized Pt@UiO-66-NH2 catalysts have the extremely low Pt loading.•Calix-3-sensitized Pt@UiO-66-NH2 catalysts exhibit high H2 production activity.•Calix-3-sensitized Pt@UiO-66-NH2 catalysts perform excellent long-term stability.A cone-calix[4]arene dye Calix-3 with four D-π-A units has been utilized to sensitize Zr-containing metal-organic framework (MOF) embedded with Pt particles, denoted as Pt@UiO-66-NH2, for photocatalytic H2 production under visible light irradiation. The structures of UiO-66-NH2, Pt-loadings, and dye-adsorbed amounts of these photocatalysts are optimized. Comparatively, Calix-3-sensitized Pt@UiO-66-NH2 catalysts with 0.65 wt% of Pt loading and 15.7 μmol/g of Calix-3 dye amount exhibit much higher hydrogen production activity (1528 μmol g−1 h−1 based on the mass of MOF or 236 mmol g−1[Pt] h−1 based on Pt mass) than that sensitized by single D-π-A M-3 dyes (516 μmol g−1 h−1 or 24 mmol g−1[Pt] h−1) under the similar photocatalytic conditions, and perform excellent stability during the long-term tests simultaneously. In view of the extremely low Pt loading, the activity based on Pt mass is one of the highest among all the reported MOF-based photocatalytic hydrogen production systems. The enhancement in hydrogen evolution efficiency and stability could be ascribed to lower tendency for aggregation, higher molar absorption coefficients, more efficient electron transfer, and better intrinsic and adsorbed stability of Calix-3 dyes. This work provides useful insights for future design and synthesis of new functional dye sensitization MOF system for photocatalytic hydrogen production.Calix-3-sensitized Pt@UiO-66-NH2 catalysts with low-cost Calix-3 dye and extremely low Pt loading exhibit an impressive visible-light photocatalytic hydrogen production activity and excellent stability during the long-term tests simultaneously.Download high-res image (148KB)Download full-size image
Co-reporter:Ling Chen, Shao-Yun Yin, Mei Pan, Kai Wu, Hai-Ping Wang, Ya-Nan Fan and Cheng-Yong Su
Journal of Materials Chemistry A 2016 vol. 4(Issue 29) pp:6962-6966
Publication Date(Web):27 Jun 2016
DOI:10.1039/C6TC01308B
A highly fluorescent HPI-based excited-state intramolecular proton transfer (ESIPT) molecule is designed and adopted as a naked-eye colorimetric sensor to distinguish methanol, ethanol and isopropanol vapors. Amplified spontaneous emission was also observed for the C1-form single crystal of the molecule attributed to its intrinsic four-level energy states.
Co-reporter:Yu-Hao Li, Ji-Jun Jiang, Yan-Zhong Fan, Zhang-Wen Wei, Cheng-Xia Chen, Hui-Juan Yu, Shao-Ping Zheng, Dieter Fenske, Cheng-Yong Su and Mihail Barboiu
Chemical Communications 2016 vol. 52(Issue 56) pp:8745-8748
Publication Date(Web):16 Jun 2016
DOI:10.1039/C6CC04420D
Fully structural interconversions between monomeric Pd2L4 and interlocked dimeric Pd4L8 cages have been investigated to elucidate their thermodynamic stability defined by their anion-guest binding behaviours.
Co-reporter:Pei-Yang Su, Yi-Fan Chen, Jun-Min Liu, Li-Min Xiao, Dai-Bin Kuang, Marcel Mayor, Cheng-Yong Su
Electrochimica Acta 2016 Volume 209() pp:529-540
Publication Date(Web):10 August 2016
DOI:10.1016/j.electacta.2016.05.122
•Incorporation of hydrophobic alkyl chains into HTMs can turn hydrophobility of the PSC film.•Hydrophobic HTMs can suppress electron recombination and thus enhance the Voc value.•Hydrophobic HTMs can prevent water penetration into the perovskite layer.•Hydrophobic HTMs can improve moisture stability of the overall cell.Two hydrophobic hole transporting materials (HTMs) carrying multiple thiophene cores of 5,7-bis(3-hexylthiophen-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine (for SP-01) or 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (for SP-02) and long alkyl substituents have been prepared through facile routes with high yields, together with the hole-transporting molecule 2,5-bis(4,4′-bis(methoxyphenyl)aminophen-4′′-yl)-3,4-ethylene dioxythiophene (H101) as reference compound. The structure-property relationships of these HTMs for perovskite solar cells have been systematically investigated. It is found that introducing hydrophobic alkyl chains into HTMs can retard interfacial charge recombination and, specifically, improve stability owing to the enhanced moisture resistance. Perovskite solar cells based on SP-01 give an overall conversion efficiency of 12.37% without, and 13.91% with the addition of FK102, respectively. These values are better than that of H101 (11.59%) and comparable to that of the standard spiro-OMeTAD (12.95%). Moreover, the devices based on hydrophobic HTMs SP-01 show better stability under ∼40% humid atmosphere than those based on H101 and spiro-OMeTAD, which paves the way for developing new HTMs combining high efficiency, low cost, and excellent stability features by appropriate structural modifications.
Co-reporter:Zhang-Wen Wei, Cheng-Xia Chen, Shao-Ping Zheng, Hai-Ping Wang, Ya-Nan Fan, Ye-Ye Ai, Mei Pan, and Cheng-Yong Su
Inorganic Chemistry 2016 Volume 55(Issue 15) pp:7311
Publication Date(Web):July 15, 2016
DOI:10.1021/acs.inorgchem.6b00429
We demonstrate that the conformation, packing mode, and blue fluorescence of a soft piezofluorochromic compound can be preserved by structurally fixing it into a solid calcium metal–organic framework (Ca-MOF, LIFM-40), which can survive pressures up to 8 MPa. DFT calculations have been combined with experimental results to indicate that the ligands adopting a specific conformation and packing without π···π interactions are the reasons for its rigidified blue emission.
Co-reporter:Hao Cui, Yingxia Wang, Yanhu Wang, Yan-Zhong Fan, Li Zhang and Cheng-Yong Su
CrystEngComm 2016 vol. 18(Issue 12) pp:2203-2209
Publication Date(Web):12 Feb 2016
DOI:10.1039/C6CE00358C
Self-assembly of a new metalloporphyrin tetracarboxylic ligand Ir(TCPP)Cl (TCPP = tetrakis(4-carboxyphenyl)porphyrin) with ZrCl4 in the presence of benzoic acid leads to the formation of a three-dimensional (3D) iridium(III)-porphyrin metal–organic framework (Ir-PMOF) with the formula of [(Zr6(μ3-O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3]·solvents (Ir-PMOF-1(Zr)), which possesses square-shaped channels of 1.9 × 1.9 nm2 (atom-to-atom distances across opposite Ir metal atoms) in three orthogonal directions as disclosed by the single-crystal X-ray diffraction analysis. Ir-PMOF-1(Zr) represents the first MOF bearing a self-supporting iridium-porphyrin catalytic framework, featuring high porosity and stability. The catalytic tests disclose that the activated Ir-PMOF-1(Zr) can promote O–H insertion with a turnover frequency (TOF) up to 4260 h−1. Ir-PMOF-1(Zr) can be recycled and reused for 10 runs without significant loss of catalytic activity, and the total turnover number (TON) for O–H insertion after 10 successive runs reaches 875.
Co-reporter:Lu-Yin Zhang, Kang Li, Mei Pan, Ya-Nan Fan, Hai-Ping Wang and Cheng-Yong Su
New Journal of Chemistry 2016 vol. 40(Issue 6) pp:5379-5386
Publication Date(Web):11 Apr 2016
DOI:10.1039/C6NJ00089D
Distinguishable d → f or f → d energy transfer processes depending on lanthanide ions are observed in isomorphous d–f heterometallic complexes containing the Ru(II) metalloligand (LRu), which lead to sensitized NIR emission (for Nd3+ and Yb3+) or enhanced red emission of LRu (for Eu3+ and Tb3+), and represent the first eye-detectable evidence of f → d energy transfer processes in Ln–Ru bimetallic complexes. Based on the systematic luminescence and decay lifetime study, cascade f → d → f energy transfer has been proposed in Ln1–Ru–Ln2 trimetallic systems for improved NIR sensitization.
Co-reporter:Ling Chen;Cheng Yan;Mei Pan;Hai-Ping Wang;Ya-Nan Fan
European Journal of Inorganic Chemistry 2016 Volume 2016( Issue 17) pp:2676-2680
Publication Date(Web):
DOI:10.1002/ejic.201600089
Multi-mode photoluminescence, including enol-emission, keto-emission, and aggregate-related emission is achieved in a ZnII coordination polymer from excited-state intramolecular proton transfer (ESIPT) ligands. Single-phase white light emission (WLE) and tunable emitting colors can be obtained by varying the suspending/grinding solvent system or temperature, which brings a brand-new model in developing multi-stimuli-responsive WLE materials.
Co-reporter:Cheng-Xia Chen;Zhangwen Wei;Ji-Jun Jiang;Yan-Zhong Fan;Shao-Ping Zheng;Chen-Chen Cao;Yu-Hao Li; Dieter Fenske ; Cheng-Yong Su
Angewandte Chemie International Edition 2016 Volume 55( Issue 34) pp:9932-9936
Publication Date(Web):
DOI:10.1002/anie.201604023
Abstract
To combine flexibility and modifiability towards a more controllable complexity of MOFs, a post-synthetic variable-spacer installation (PVSI) strategy is used to implement kinetic installation/ uninstallation of secondary ligands into/from a robust yet flexible proto-Zr-MOF. This PVSI process features precise positioning of spacers with different length, size, number, and functionality, enabling accurate fixation of successive breathing stages and fine-tuning of pore surface. It shows unprecedented synthetic tailorability to create complicated MOFs in a predictable way for property modification, for example, CO2 and R22 adsorption/separation, thermal/chemical stability, and extended breathing behavior.
Co-reporter:Cheng-Xia Chen;Zhangwen Wei;Ji-Jun Jiang;Yan-Zhong Fan;Shao-Ping Zheng;Chen-Chen Cao;Yu-Hao Li; Dieter Fenske ; Cheng-Yong Su
Angewandte Chemie 2016 Volume 128( Issue 34) pp:10086-10090
Publication Date(Web):
DOI:10.1002/ange.201604023
Abstract
To combine flexibility and modifiability towards a more controllable complexity of MOFs, a post-synthetic variable-spacer installation (PVSI) strategy is used to implement kinetic installation/ uninstallation of secondary ligands into/from a robust yet flexible proto-Zr-MOF. This PVSI process features precise positioning of spacers with different length, size, number, and functionality, enabling accurate fixation of successive breathing stages and fine-tuning of pore surface. It shows unprecedented synthetic tailorability to create complicated MOFs in a predictable way for property modification, for example, CO2 and R22 adsorption/separation, thermal/chemical stability, and extended breathing behavior.
Co-reporter:Haoliang Liu, Juan Feng, Jianyong Zhang, Philip W. Miller, Liuping Chen and Cheng-Yong Su
Chemical Science 2015 vol. 6(Issue 4) pp:2292-2296
Publication Date(Web):18 Feb 2015
DOI:10.1039/C5SC00314H
A novel dynamic covalent gel strategy is reported to immobilize an asymmetric catalyst within the channels of a microfluidic flow reactor. A layer of a catalytically active Mn–salen dynamic covalent imine gel matrix was coated onto a functionalized capillary. Mn–salen active moiety was incorporated into dynamic covalent imine gel matrix via the reaction of a chiral Mn–salen dialdehyde unit with a tetraamine linker. The catalytic activity of the capillary reactor has been demonstrated in enantioselective kinetic resolution of secondary alcohols.
Co-reporter:Lianfen Chen, Tao Yang, Hao Cui, Tao Cai, Li Zhang and Cheng-Yong Su
Journal of Materials Chemistry A 2015 vol. 3(Issue 40) pp:20201-20209
Publication Date(Web):28 Aug 2015
DOI:10.1039/C5TA05592J
Self-assembly of dirhodium(II) tetraacetate (Rh2(OAc)4) with a dicarboxylic acid 3,3′-(1,3-phenylenebis(ethyne-2,1-diyl))dibenzoic acid (H2pbeddb) gives rise to a metal–organic cage (MOC) containing Rh–Rh bonds with the formula of [Rh4(pbeddb)4(H2O)2(DMAC)2] (MOC-Rh-1). Single-crystal X-ray diffraction analysis reveals that MOC-Rh-1 shows a lantern-type cage structure, in which a pair of Rh2(CO2)4 paddlewheels is linked by four diacid ligands. The dimensions of the inner cavity of MOC-Rh-1 are 9.5 × 14.8 Å2 (atom-to-atom distances across opposite metal and phenyl groups of pbeddb2−). In the solid phase, the cages are aligned by π–π stacking to form one-dimensional channels (9.5 × 11.1 Å2) through cage windows. Therefore, the crystalline samples of MOC-Rh-1 are porous with the inner and outer cavities of the cages accessible under the heterogeneous condition. MOC-Rh-1 has been fully characterized by EA, TGA, PXRD, IR, UV-vis and XPS measurements. The catalytic tests disclose that activated MOC-Rh-1 is effective in the intramolecular C–H amination of vinyl, dienyl and biaryl azides, leading to the formation of indoles, pyrroles and carbazoles, respectively, and the porous catalyst can be recycled easily and used for at least nine runs without significant loss of activity. In the nine runs, the conversions were in the range of 93–99%, whereas in the tenth run, the conversion was reduced to 78%.
Co-reporter:Yi-Fan Chen, Jun-Min Liu, Jian-Feng Huang, Li-Lin Tan, Yong Shen, Li-Min Xiao, Dai-Bin Kuang and Cheng-Yong Su
Journal of Materials Chemistry A 2015 vol. 3(Issue 15) pp:8083-8090
Publication Date(Web):03 Mar 2015
DOI:10.1039/C5TA00332F
Two novel arylamine-free organic compounds (CYF1 and CYF2) incorporating a substituted benzo[1,2-b:4,5-b′]dithiophene unit as the electron donor were synthesized and used as sensitizers for dye-sensitized solar cells (DSSCs). The relationship between the chemical structure and photovoltaic performance was investigated. A higher molar absorption coefficient, longer electron lifetime, and larger adsorption amount were observed for sensitizer CYF1, which contains a single π bridge and anchoring unit, compared with CYF2 with twin π bridges and anchoring units. As a result, under standard global AM 1.5 solar conditions, the device based on CYF1 sensitizer gave a higher conversion efficiency of 8.02% than that based on CYF2. This is the highest value for amine-free organic sensitizers with no strong donor units. Moreover, the CYF1- and CYF2-sensitized DSSCs exhibited excellent stability under 1000 W m2 light soaking at 60 °C for 600 h. This is the first example of organic sensitizers based on benzo[1,2-b:4,5-b′]dithiophene donors for efficient dye-sensitized solar cells.
Co-reporter:Shuhai Wang, Yanan Fan, Minqi Chen, Yanyu Xie, Dawei Wang and Cheng-Yong Su
Journal of Materials Chemistry A 2015 vol. 3(Issue 16) pp:8250-8255
Publication Date(Web):18 Mar 2015
DOI:10.1039/C5TA00904A
Porous Co–P–Pd nanotube arrays (NTAs) are prepared and used for catalyzing the hydrolysis of alkaline NaBH4 solution to generate H2. Benefiting from the unique porous structure and synergistic effect, the Co–P–Pd NTAs show a maximum hydrogen generation rate of 4216 mL per min per g catalyst and good cyclic stability.
Co-reporter:Bin-Bin Du, Yi-Xuan Zhu, Mei Pan, Mei-Qin Yue, Ya-Jun Hou, Kai Wu, Lu-Yin Zhang, Ling Chen, Shao-Yun Yin, Ya-Nan Fan and Cheng-Yong Su
Chemical Communications 2015 vol. 51(Issue 63) pp:12533-12536
Publication Date(Web):29 Jun 2015
DOI:10.1039/C5CC04468E
Direct white-light emission and further a dual-channel readable barcode module in both visible and NIR region was established by single-component homo-metallic Pr(III)-MOF crystals for the first time.
Co-reporter:Jian-Feng Huang, Jun-Min Liu, Pei-Yang Su, Yi-Fan Chen, Yong Shen, Li-Min Xiao, Dai-Bin Kuang, Cheng-Yong Su
Electrochimica Acta 2015 Volume 174() pp:494-501
Publication Date(Web):20 August 2015
DOI:10.1016/j.electacta.2015.06.023
•Four novel thiocyanate-free cyclometalated ruthenium sensitizer were conveniently synthesized.•The D-CF3-sensitized DSSCs show higher efficiency compared to N719 based cells.•The DSSCs based on D-CF3 and D-bisCF3 sensitizers exhibit excellent long-term stability.•The diverse cyclometalated Ru complexes can be developed as high-performance sensitizers for use in DSSC.Four novel thiocyanate-free cyclometallted Ru(II) complexes, D-bisCF3, D-CF3, D-OMe, and D-DPA, with two 4,4′-dicarboxylic acid-2,2′-bipyridine together with a functionalized phenylpyridine ancillary ligand, have been designed and synthesized. The effect of different substituents (R = bisCF3, CF3, OMe, and DPA) on the ancillary C^N ligand on the photophysical properties and photovoltaic performance is investigated. Under standard global AM 1.5 solar conditions, the device based on D-CF3 sensitizer gives a higher conversion efficiency of 8.74% than those based on D-bisCF3, D-OMe, and D-DPA, which can be ascribed to its broad range of visible light absorption, appropriate localization of the frontier orbitals, weak hydrogen bonds between -CF3 and -OH groups at the TiO2 surface, moderate dye loading on TiO2, and high charge collection efficiency. Moreover, the D-bisCF3 and D-CF3 based DSSCs exhibit good stability under 100 mW cm−2 light soaking at 60 °C for 400 h.
Co-reporter:Qing-Yuan Yang, Mei Pan, Shi-Chao Wei, Kang Li, Bin-Bin Du, and Cheng-Yong Su
Inorganic Chemistry 2015 Volume 54(Issue 12) pp:5707-5716
Publication Date(Web):March 30, 2015
DOI:10.1021/acs.inorgchem.5b00271
Multicolored photoluminescence tuning in a single-phase material has invaluable potential in display and security applications. By deliberate design of a multifunctional antenna ligand and precise control of mixed metal ionic compositions in lanthanide metal–organic frameworks (Ln-MOFs), we achieved dichromatic fine-tuning among red, green, or blue primary colors through growth of a series of isomorphous Ln-MOF crystals·solvents of formula [LnnLn′1–n(TTP)2·H2O]Cl3 (Ln = Ln′ = Eu, Tb, and Gd, 1–3; Ln = Eu, Ln′ = Tb, 4–8; Ln = Gd, Ln′ = Eu, 9–11; Ln = Gd, Ln′ = Tb, 12–14; 0 < n < 1; TTP = 1′,1″-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)tris(pyridine-4(1H)-one)). The linear dependence of the emissions were analyzed, and the mathematical matrix models were established, which are useful to control the synthetic conditions and to predict the color chromaticity coordinates under varied excitation wavelengths. The potential relevance of these multicolored photoluminescent Ln-MOFs to barcoded materials was demonstrated.
Co-reporter:Lu-Yin Zhang, Ya-Jun Hou, Mei Pan, Ling Chen, Yi-Xuan Zhu, Shao-Yun Yin, Guang Shao and Cheng-Yong Su
Dalton Transactions 2015 vol. 44(Issue 34) pp:15212-15219
Publication Date(Web):13 Apr 2015
DOI:10.1039/C5DT00545K
Four Ru(II)/Ir(III) metalloligands have been designed and synthesized from polypyridine and bibenzimidazole (BiBzIm) organic ligands, which show strong visible light absorption via metal-to-ligand charge transfer (MLCT) transitions. Nd/Yb(III) complexes were further assembled from these Ru(II)/Ir(III) metalloligands, and Ln(III)-centered NIR emissions can be efficiently sensitized by 3MLCT states of the metalloligands in the visible-light region. The energy transfer rates for the complexes are generally in the order Nd > Yb, which is due to the better matching between 3MLCT states of Ru(II)/Ir(III) metalloligands and densely distributed excited states of Nd(III) ions. Long decayed lifetimes on a μs scale and high quantum yields up to 1% are obtained in these lanthanide complexes, suggesting that the Ru(II)/Ir(III) metalloligands can serve as a good visible light harvesting antenna to efficiently sensitize Ln(III)-based NIR luminescence.
Co-reporter:Jian-Feng Huang, Jun-Min Liu, Li-Lin Tan, Yi-Fan Chen, Yong Shen, Li-Min Xiao, Dai-Bin Kuang, Cheng-Yong Su
Dyes and Pigments 2015 Volume 114() pp:18-23
Publication Date(Web):March 2015
DOI:10.1016/j.dyepig.2014.10.022
•Organic D-D-π-A type dyes based on carbazole and thiophene were synthesized.•Incorporation of long alkyl chain enhances the molar extinction coefficients.•Introduction of long alkyl chain suppresses the charge recombination with electrolyte.•The properties of the dyes were enhanced by introducing the EDOT group in sensitizer linker.Four novel D-D-π-A type organic dyes (DWH1–DWH4) were designed and synthesized, in which 3,6-bis(thiophene or hexylthiophene)-disubstituted carbazole moieties were used as the electron donor, bithiophene units or their derivatives as the π-conjugated bridge, and a cyanoacrylic acid group as the electron acceptor. The photovoltaic performance data indicate that the tuning of the Jsc and Voc values can be conveniently accomplished by incorporation of long alkyl chains into sensitizer, which not only improves the molar extinction coefficients of the absorption and enhances the solubility but also increases the electron lifetime by leading to an effective spatial separation of the charges.Novel carbazole based dyes with long alkyl chains have been synthesized and characterized. The electro-optical properties of these dyes can be tuned by changing the π-linker structures. Incorporation of long alkyl chains into sensitizer not only enhances the molar extinction coefficients of the absorption but also suppresses the charge recombination with electrolyte.
Co-reporter:Zhao Zhang, Heini Feng, Lin Liu, Chao Yu, Xingqiang Lü, Xunjin Zhu, Wai-Kwok Wong, Richard A. Jones, Mei Pan and Chengyong Su
Dalton Transactions 2015 vol. 44(Issue 13) pp:6229-6241
Publication Date(Web):19 Feb 2015
DOI:10.1039/C5DT00141B
In the series of homo-leptic trinuclear complexes {[Ln3(L)4Cl4(MeOH)(H2O)]·Cl} (Ln = La, 1; Ln = Eu, 2; Ln = Tb, 3 or Ln = Gd, 4) self-assembled from the allyl-modified benzimidazole-type ligand HL (4-allyl-2-(1H-benzo[d]imidazol-2-yl)-6-methoxyphenol) and LnCl3·6H2O, a suitable energy level match endows efficient green luminescence (Φoverall = 72%) of Tb3-arrayed complex 3. The copolymerization between each of these complex monomers 1–4 and CC-containing MMA (methyl methacrylate) or NBE (norbornene) shows that degradative chain transfer of the terminal four flexible allyl groups within restrains their radical polymerization with MMA while it does not hinder their effective ring-opening metathesis polymerization (ROMP) with NBE. Thus, two kinds of PMMA-supported doping hybrid materials 1@PMMA, 2@PMMA, 3@PMMA and 4@PMMA and PNBE-supported metallopolymer-type hybrid materials Poly(NBE-1), Poly(NBE-2), Poly(NBE-3) and Poly(NBE-4) are obtained, respectively. Especially for both 3@PMMA and Poly(NBE-3) with high color-purity characteristic green emission of Tb3+ ions, improved physical properties including significantly enhanced luminescence (Φoverall = 76% or 83%) are observed, and covalent-bonding endows a higher-concentration self-quenching as compared to physical doping.
Co-reporter:Lianfen Chen, Jian Kang, Hao Cui, Yingxia Wang, Lan Liu, Li Zhang and Cheng-Yong Su
Dalton Transactions 2015 vol. 44(Issue 27) pp:12180-12188
Publication Date(Web):19 Feb 2015
DOI:10.1039/C4DT03782K
A series of homochiral metal–organic cages (MOCs) have been obtained from self-assembly of Cu(II) salts with chiral N,N′-(bicyclo[2,2,2]oct-7-ene-tetracarboxylic)-bis-amino acids. Single-crystal X-ray diffraction analyses reveal that these compounds show a lantern-type cage structure, in which one pair of Cu2(CO2)4 paddlewheels is linked by four diacid ligands. The resulting homochiral cages have been fully characterized by EA, TOF-MS, TGA, VTPXRD, IR, UV, and CD measurements. The catalytic tests reveal that these Cu(II) cages are effective in cyclopropanation with excellent diastereoselectivity (up to 99:1 E/Z). In addition, the cage catalysts can promote the aziridination reaction with PhINNs.
Co-reporter:Ling Chen, Cheng Yan, Mei Pan, Yuan-Zhong Fan, Lu-Yin Zhang, Shao-Yun Yin, Ya-Jun Hou, Kai Wu, Ji-Jun Jiang and Cheng-Yong Su
New Journal of Chemistry 2015 vol. 39(Issue 11) pp:9029-9029
Publication Date(Web):05 Oct 2015
DOI:10.1039/C5NJ90044A
Correction for ‘Semidirected versus holodirected coordination and single-component white light luminescence in Pb(II) complexes’ by Ling Chen et al., New J. Chem., 2015, 39, 5287–5292.
Co-reporter:Ling Chen, Cheng Yan, Mei Pan, Yuan-Zhong Fan, Lu-Yin Zhang, Shao-Yun Yin, Ya-Jun Hou, Kai Wu, Ji-Jun Jiang and Cheng-Yong Su
New Journal of Chemistry 2015 vol. 39(Issue 7) pp:5287-5292
Publication Date(Web):29 Apr 2015
DOI:10.1039/C5NJ00720H
2-Methyl-8-hydroxyquinoline (HMq) and the tripodal ligands 4,4′,4′′-(2,2′,2′′-nitrilotris (methylene)tris(1H-benzo[d]imidazole-2,1-diyl)tris(methylene))tribenzonitrile (triBZ-NTB) and 4,4′,4′′-(2,2′,2′′-nitrilotris(methylene)tris(1H-benzo[d]imidazole-2,1-diyl)tris(methylene))tribenzoic acid (H3triCB-NTB) were used individually to assemble a hetero-nuclear, a tetra-nuclear and two mono-nuclear Pb(II) complexes. The Pb(II) coordination centers in two of these complexes were observed to display semidirected coordination with the ligands and counter anions (small solvent molecules), whereas the other two complexes showed holodirected coordination, together leading to varied coordination geometries. The combination of ligand-to-metal charge-transfer (LMCT) and metal-centered (MC) emissions in the semidirected Pb(II) complexes resulted in single-component white light luminescence.
Co-reporter:Li-Lin Tan;Dr. Jun-Min Liu;Dr. Shao-Yong Li; Li-Min Xiao; Dai-Bin Kuang; Cheng-Yong Su
ChemSusChem 2015 Volume 8( Issue 2) pp:
Publication Date(Web):
DOI:10.1002/cssc.201403048
Abstract
Invited for the cover of this issue is the group of Jun-Min Liu and Cheng-Yong Su at Sun Yat-Sen University. The image shows that cone-calix[4]arene-based dye flowers can develop in the field of dye-sensitized solar cells as sunflowers thrive under sunshine. The Full Paper itself is available at 10.1002/cssc.201402401
Co-reporter:Li-Lin Tan;Dr. Jun-Min Liu;Dr. Shao-Yong Li; Li-Min Xiao; Dai-Bin Kuang; Cheng-Yong Su
ChemSusChem 2015 Volume 8( Issue 2) pp:
Publication Date(Web):
DOI:10.1002/cssc.201403047
Co-reporter:Li-Lin Tan;Dr. Jun-Min Liu;Dr. Shao-Yong Li; Li-Min Xiao; Dai-Bin Kuang; Cheng-Yong Su
ChemSusChem 2015 Volume 8( Issue 2) pp:280-287
Publication Date(Web):
DOI:10.1002/cssc.201402401
Abstract
Three cone-calix[4]arene-based sensitizers (Calix-1–Calix-3) with multiple donor–π–acceptor (D–π–A) moieties are designed, synthesized, and applied in dye-sensitized solar cells (DSSCs). Their photophysical and electrochemical properties are characterized by measuring UV/Vis absorption and emission spectra, cyclic voltammetry, and density functional theory (DFT) calculations. Calix-3 has excellent thermo- and photostability, as illustrated by thermogravimetric analysis (TGA) and dye-aging tests, respectively. Importantly, a DSSC using the Calix-3 dye displays a conversion efficiency of 5.48 % in under standard AM 1.5 Global solar illumination conditions, much better than corresponding DSSCs that use the rod-shaped dye M-3 with a single D–π–A chain (3.56 %). The dyes offer advantages in terms of higher molar extinction coefficients, longer electron lifetimes, better stability, and stronger binding ability to TiO2 film. This is the first example of calixarene-based sensitizers for efficient dye-sensitized solar cells.
Co-reporter:Jiewei Liu, Lianfen Chen, Hao Cui, Jianyong Zhang, Li Zhang and Cheng-Yong Su
Chemical Society Reviews 2014 vol. 43(Issue 16) pp:6011-6061
Publication Date(Web):29 May 2014
DOI:10.1039/C4CS00094C
This review summarizes the use of metal–organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal–organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.
Co-reporter:Hong-Yan Chen, Yang-Fan Xu, Dai-Bin Kuang and Cheng-Yong Su
Energy & Environmental Science 2014 vol. 7(Issue 12) pp:3887-3901
Publication Date(Web):04 Sep 2014
DOI:10.1039/C4EE02213K
Macroporous structures have attracted great interest for a wide range of applications due to their unique structure-determined physical and chemical properties. In regard to the inherent low surface area, decoration of macroporous structures with small building blocks (including nanoparticles, nanorods, nanowires, nanosheets, etc.) to form macroporous composite materials therefore have been highly pursued very recently. In this review, we summarize the recent advances in synthesis of hierarchical macroporous composite materials and their potential applications as photoelectrode materials for dye-sensitized solar cells (DSSCs), quantum dot-sensitized solar cells (QDSSCs) and photoelectrochemical (PEC) cells.
Co-reporter:Shi-Chao Wei;Mei Pan;, Kang Li;Sujuan Wang;Jianyong Zhang
Advanced Materials 2014 Volume 26( Issue 13) pp:2072-2077
Publication Date(Web):
DOI:10.1002/adma.201304404
Co-reporter:Kang Li ; Lu-Yin Zhang ; Cheng Yan ; Shi-Chao Wei ; Mei Pan ; Li Zhang
Journal of the American Chemical Society 2014 Volume 136(Issue 12) pp:4456-4459
Publication Date(Web):March 10, 2014
DOI:10.1021/ja410044r
Stepwise synthesis of nanosized Pd−Ru heteronuclear metal–organic cages from predesigned redox- and photo-active Ru(II)-metalloligand and naked Pd(II) ion is described. The resulting cage shows rhombododecahedral shape and contains a 5350 Å3 cavity and 12 open windows, facilitating effective trapping of both polar and nonpolar guest molecules. Protection of photosensitive guests against UV radiation is studied.
Co-reporter:Li-Lin Tan, Jian-Feng Huang, Yong Shen, Li-Min Xiao, Jun-Min Liu, Dai-Bin Kuang and Cheng-Yong Su
Journal of Materials Chemistry A 2014 vol. 2(Issue 24) pp:8988-8994
Publication Date(Web):17 Apr 2014
DOI:10.1039/C4TA01351D
Two new D–D–π–π–A type stable organic sensitizers, DT3 and DW3, were successfully synthesized for dye-sensitized solar cells (DSSCs). DT3 displayed η values of 10.03% and 8.05% in liquid and quasi-solid-state DSSCs, respectively, under standard global 1.5 solar conditions, offering an example achieving the highest efficiency to date in quasi-solid-state DSSCs based on pure organic dyes.
Co-reporter:Ying Xiong, Yan-Zhong Fan, Rui Yang, Sha Chen, Mei Pan, Ji-Jun Jiang and Cheng-Yong Su
Chemical Communications 2014 vol. 50(Issue 93) pp:14631-14634
Publication Date(Web):22 Sep 2014
DOI:10.1039/C4CC06697A
By stepwise functionalization of a T-shaped ligand with amide and N-oxide groups, we obtained a MOF with drastically strengthened CO2–framework interactions, induced by a “open donor sites” (ODSs) effect, resulting in a high heat of adsorption and high CO2/CH4, CO2/CO and CO2/N2 separation selectivities at room temperature.
Co-reporter:Qing-Yuan Yang, Kai Wu, Ji-Jun Jiang, Chien-Wei Hsu, Mei Pan, Jean-Marie Lehn and Cheng-Yong Su
Chemical Communications 2014 vol. 50(Issue 57) pp:7702-7704
Publication Date(Web):30 May 2014
DOI:10.1039/C4CC01763C
Direct white-light emission was first achieved in a single phase material of a Dy(III) metal–organic framework, which also shows tunable yellow-to-blue photoluminescence upon variation of excitation wavelengths.
Co-reporter:Qing-Yuan Yang, Mei Pan, Shi-Chao Wei, Chien-Wei Hsu, Jean-Marie Lehn and Cheng-Yong Su
CrystEngComm 2014 vol. 16(Issue 28) pp:6469-6475
Publication Date(Web):13 May 2014
DOI:10.1039/C4CE00586D
A new semi-rigid tripodal ligand, namely 1,1′,1′′-((2,4,6-triethylbenzene-1,3,5 triyl)tris(methylene))tris(pyridin-4(1H)-one) (L1), has been prepared by direct alkylation of 4-hydroxypyridine at the nitrogen site with 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene. The tripodal ligand has been used for the assembly of a series of isomorphous lanthanide metal–organic frameworks (Ln-MOFs) [Ln(L1)·(NO3)3]·nH2O (Ln = Eu (1), Tb (2), Sm (3), Ce (4), Gd (5); n = 3 or 4) which exhibit an unusual non-interpenetrated (10,3)-d (or utp net) topology. The photophysical properties of these lanthanide MOFs have been assessed, in which the Tb3+ complex 2 displays bright green luminescence with quite high efficiency (Φoverall = 50%) and a long excited state lifetime (τobs = 1.1 ms).
Co-reporter:Mei Pan and Cheng-Yong Su
CrystEngComm 2014 vol. 16(Issue 34) pp:7847-7859
Publication Date(Web):09 May 2014
DOI:10.1039/C4CE00616J
The Borromean link constitutes an intriguing type of entanglement and knot in both discrete coordination architectures (Borromeate or Borromeand) and infinite coordination assemblies (Borromean networks), and is characteristic of nontrivial three-ring links which are inseparable as a whole while cleavage of any ring makes the whole fall apart. This highlight paper covers recent advances in the assembly of coordination supramolecular structures showing Borromean-linking topological character.
Co-reporter:Yao-Wei Xu, Li-Lin Tan, Jun-Min Liu, Li-Min Xiao, Shao-Yong Li and Cheng-Yong Su
RSC Advances 2014 vol. 4(Issue 53) pp:28046-28051
Publication Date(Web):16 Jun 2014
DOI:10.1039/C4RA04074K
A modified calix[4]arene based receptor 2, conjugated with four bithiophene–cyanoacrylic acid groups, not only recognizes acidic amino acids (Asp and Glu) by quenching fluorescence, but also shows highly selective sensing for basic amino acids (Lys and Arg) by turning on fluorescence in sodium phosphate buffer solution without any organic solvent. The UV-Vis spectroscopy binding analysis and ESI-MS studies indicate that the above complexes have a 1:1 stoichiometry. 1H NMR and molecular modeling studies suggest a supramolecular complex structure like the relationship between a lid and cup, but not a typical host-guest relationship of the cavity. A plausible mechanism involving intramolecular charge transfer (ICT) is proposed.
Co-reporter:Minjuan Lin, Haoliang Liu, Philip W. Miller, Jianyong Zhang and Cheng-Yong Su
New Journal of Chemistry 2014 vol. 38(Issue 8) pp:3755-3761
Publication Date(Web):29 May 2014
DOI:10.1039/C4NJ00445K
Post-modification of supramolecular assemblies via covalent capture is an important strategy for the fabrication of functional materials. This paper describes the synthesis of supramolecular nanotubes with appended pyridyl groups based on N,N′,N′′-tris(3-methylpyridyl)trimesic amide (TMPTA), and their successful post-modification by 1,4-bis(bromomethyl)benzene. The original tubular morphology of the TMPTA nanotubes was found to stay intact following the modification process. The modified nanotubes are resistant to attack by strong acids and bases. The continuous network of covalent bonds throughout the tubular network is responsible for this stability. The formation of pyridinium cations upon modification results in positively charged surfaces of nanotubes that were found to be highly effective adsorbents for a range of anionic dyes, demonstrating both high adsorption capacity and selectivities over cationic and neutral dye species. These materials can be reused for dye capture without losses in their capture ability.
Co-reporter:Li-Lin Tan, Li-Jun Xie, Yong Shen, Jun-Min Liu, Li-Min Xiao, Dai-Bin Kuang, Cheng-Yong Su
Dyes and Pigments 2014 100() pp: 269-277
Publication Date(Web):
DOI:10.1016/j.dyepig.2013.09.025
Co-reporter:Minjuan Lin, Sujuan Wang, Jianyong Zhang, Weijun Luo, Haoliang Liu, Wei Wang, Cheng-Yong Su
Journal of Molecular Catalysis A: Chemical 2014 Volume 394() pp:33-39
Publication Date(Web):15 November 2014
DOI:10.1016/j.molcata.2014.06.039
•A porous imidazolium polymeric network has been prepared.•Its complexation with palladium yielded a Pd-NHC porous polymeric network.•The Pd-NHC network showed ability to absorb both hydrophilic and aromatic guests.•The Pd-NHC network catalyzed carbon–carbon coupling reactions in a heterogeneous way with excellent recyclability.A porous imidazolium polymeric network was synthesized via alkylation of tetrakis-[4-(1H-imidazole-1-yl)phenyl]methane with 1,4-bis(bromomethyl)benzene. Its complexation with palladium yielded a Pd-NHC porous polymeric network, namely Pd-pNHC. Pd-pNHC showed selective uptake of CO2 over N2 due to its polar surface. Pd-pNHC has a BET specific surface area of 308 m2 g−1 and a micropore volume of 0.190 cm3 g−1. Pd-pNHC showed ability to absorb both hydrophilic and aromatic guests (MeOH, EtOH and benzene). Pd(II) catalytically active centers within the porous polymeric network were readily accessible to substrates as demonstrated in Suzuki–Miyaura coupling reactions. High yields were achieved in the coupling reactions of various arylbromides under mild conditions. Additionally, Pd-pNHC catalyzed the reactions in a heterogeneous way and the catalyst could be used for at least ten times without loss of activity.
Co-reporter:Qi-Ting He, Xiang-Ping Li, Lian-Fen Chen, Li Zhang, Wei Wang, and Cheng-Yong Su
ACS Catalysis 2013 Volume 3(Issue 1) pp:1
Publication Date(Web):November 13, 2012
DOI:10.1021/cs300640r
The intermolecular catalysis toward the oxidation of hydrocarbons has been studied with a series of nanoscale coordination cages [CuI4L4]4+, which are characteristic of the inherent catalytic activity by installing multiple Cu+ redox active ions on the cage vertices. The catalytic reactions take place out-cage on the surface active Cu+ sites, while the catalytic activity can be modulated in-cage by the guest anions, establishing an unprecedented host–guest regulable catalysis structural model for coordination cages in the sense of supramolecular catalysis. The catalytic behavior and mechanism, reactivity-structure relationship, and recyclable use of the cage catalysts have been thoroughly explored, in an effort to find the way to achieving robust catalysis through careful tuning of the solution stability and redox activity of cage structures by changing size and shape of guest anions.Keywords: cage compounds; copper; C−H activation; host−guest system; supramolecular catalysis
Co-reporter:Lei Fu, Yu Liu, Mei Pan, Xiao-Jun Kuang, Cheng Yan, Kang Li, Shi-Chao Wei and Cheng-Yong Su
Journal of Materials Chemistry A 2013 vol. 1(Issue 30) pp:8575-8580
Publication Date(Web):10 May 2013
DOI:10.1039/C3TA11157A
A microporous coordination framework formed by hydrogen-bonding directed assembly of Cu(II) hexanuclear rings can act as a host for iodine accumulation in an aqueous solution. Various iodine species, I−, I3− or I2, are able to be trapped in the hydrophilic voids of the crystals via a single-crystal-to-single-crystal ion-exchange process. The chemical nature of the iodine species encapsulated inside the coordination framework have been established by single crystal and powder XRD, IR, XPS, EA, TG and iodometric methods. Furthermore, the accumulated iodine species can be easily extracted from the crystals by organic solvents. The kinetics of I3− release from the crystals by extraction with ethanol has been studied.
Co-reporter:Gao-Ren Li, Han Xu, Xue-Feng Lu, Jin-Xian Feng, Ye-Xiang Tong and Cheng-Yong Su
Nanoscale 2013 vol. 5(Issue 10) pp:4056-4069
Publication Date(Web):19 Mar 2013
DOI:10.1039/C3NR00607G
Electrochemical synthesis represents a highly efficient method for the fabrication of nanostructured energy materials, and various nanostructures, such as nanorods, nanowires, nanotubes, nanosheets, dendritic nanostructures, and composite nanostructures, can be easily fabricated with advantages of low cost, low synthetic temperature, high purity, simplicity, and environmental friendliness. The electrochemical synthesis, characterization, and application of electrochemical energy nanomaterials have advanced greatly in the past few decades, allowing an increasing understanding of nanostructure-property–performance relationships. Herein, we highlight some recent progress in the electrochemical synthesis of electrochemical energy materials with the assistance of additives and templates in solution or grafted onto metal or conductive polymer supports, with special attention to the effects on surface morphologies, structures and, more importantly, electrochemical performance. The methodology for preparing novel electrochemical energy nanomaterials and their potential applications has been summarized. Finally, we outline our personal perspectives on the electrochemical synthesis and applications of electrochemical energy nanomaterials.
Co-reporter:Hong-Yan Chen, Teng-Long Zhang, Jie Fan, Dai-Bin Kuang, and Cheng-Yong Su
ACS Applied Materials & Interfaces 2013 Volume 5(Issue 18) pp:9205
Publication Date(Web):August 20, 2013
DOI:10.1021/am402853q
Ultraporous anatase TiO2 nanorods with a composite structure of mesopores and macropores fabricated via a simple microemulsion electrospinning approach were first used as photoanode materials for high-efficiency dye-sensitized solar cells (DSSCs). The special multiscale porous structure was formed by using low-cost paraffin oil microemulsion droplets as the soft template, which can not only provide enhanced adsorption sites for dye molecules but also facilitate the electrolyte diffusion. The morphology, porosity, and photovoltaic and electron dynamic characteristics of the porous TiO2 nanorod based DSSCs were investigated in detail by scanning electron microscopy (SEM), N2 sorption measurements, current density–voltage (J–V) curves, UV–vis diffuse reflectance spectra, electrochemical impedance spectroscopy (EIS), intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS), and open-circuit voltage decay (OCVD) measurements. The results revealed that, although fewer amounts of dyes were anchored on the porous TiO2 nanorod films, they exhibited stronger light scattering ability, fast electrolyte diffusion, and extended electron lifetime compared to the commercial P25 nanoparticles. A power conversion efficiency of 6.07% was obtained for the porous TiO2 nanorod based DSSCs. Moreover, this value can be further improved to 8.53% when bilayer structured photoanode with porous TiO2 nanorods acting as the light scattering layer was constructed. This study demonstrated that the porous TiO2 nanorods can work as promising photoanode materials for DSSCs.Keywords: dye-sensitized solar cells; electron lifetime; light scattering; porous structure; TiO2 nanorods;
Co-reporter:Tao Yang, Hao Cui, Changhe Zhang, Li Zhang, and Cheng-Yong Su
Inorganic Chemistry 2013 Volume 52(Issue 15) pp:9053-9059
Publication Date(Web):July 25, 2013
DOI:10.1021/ic4012229
The robustly porous metal–organic framework MOF–Cu2I2(BTTP4) (BTTP4 = benzene-1,3,5-triyl triisonicotinate) was shown to work as an efficiently heterogeneous catalyst for the three-component coupling of sulfonyl azides, alkynes, and amines, leading to the formation of N-sulfonyl amidines in good yields. MOF–Cu2I2(BTTP4) can be recycled by simple filtration and reused at least four times without any loss in yield. Studies of the ligand effects on the three-component coupling reactions showed that BTTP4 could enhance the rate, as well as the chemoselectivity, when aromatic alkynes were employed. The catalytic process has been thoroughly studied by means of single-crystal and powder X-ray diffraction, gas and solvent adsorption, in situ 1H NMR and FT-IR spectroscopy, X-ray photoelectron spectra (XPS), and ICP analysis of Cu leaching.
Co-reporter:Sujuan Wang, Qiuli Yang, Jianyong Zhang, Xuepeng Zhang, Cunyuan Zhao, Long Jiang, and Cheng-Yong Su
Inorganic Chemistry 2013 Volume 52(Issue 8) pp:4198-4204
Publication Date(Web):March 26, 2013
DOI:10.1021/ic301781n
A charge-separated metal–organic framework (MOF) has been successfully synthesized from an imidazolium tricarboxylate ligand, N-(3,5-dicarboxylphenyl)-N′-(4-carboxylbenzyl)imidazolium chloride (DCPCBImH3Cl), and a zinc(II) dimeric secondary building unit, namely, DCPCBim-MOF-Zn, which shows an unprecedented 3,6-connected two-dimensional net topology with the point (Schläfli) symbol (42.6)2(44.69.82). The framework contains one-dimensional highly polar channels, and density functional theory calculations show that positive charges are located on the imidazolium/phenyl rings and negative charges on the carboxylate moieties. The charge-separated nature of the pore surface has a profound effect in their adsorption behavior, resulting in remarkable hysteretic sorption of various gases and vapors. For CO2, the hysteretic sorption was observed to occur even up to 298 K. Additionally, trace chloride anions present in the pore channels are able to modulate the gas-sorption behavior.
Co-reporter:Hong-Yan Chen, Ling Lin, Xiao-Yun Yu, Kang-Qiang Qiu, Xian-Yong Lü, Dai-Bin Kuang, Cheng-Yong Su
Electrochimica Acta 2013 Volume 92() pp:117-123
Publication Date(Web):1 March 2013
DOI:10.1016/j.electacta.2013.01.025
Highly conductive hydrogel polysulfide electrolyte is first fabricated using dextran as gelator and used as quasi-solid-state electrolyte for quantum dot-sensitized solar cells (QDSSCs). The hydrogel electrolyte with gelator concentration of 15 wt% shows almost the same conductivity as the liquid one. Moreover, its liquid state at elevated temperature allow for the well penetration into the pores in electrodeposited CdS/CdSe co-sensitized TiO2 photoanode. This gel electrolyte based QDSSC exhibits power conversion efficiency (η) of 3.23% under AG 1.5 G one sun (100 mW cm−2) illumination, slightly lower than that of liquid electrolyte based cell (3.69%). The dynamic electron transfer mechanism of the gel and liquid electrolyte based QDSSC are examined by electrochemical impedance spectroscopy (EIS) and controlled intensity modulated photocurrent/photovoltage spectroscopy (CIMPS/IMVS). It is found that the electron transport in gel electrolyte based cell is much faster than the liquid electrolyte based cell but it tends to recombine more easily than the latter. However, these differences fade away with increasing the light intensity, showing declining electron collection efficiency at higher light intensity illumination. As a result, a conversion efficiency of 4.58% is obtained for the gel electrolyte based quasi-solid-state QDSSC under 0.12 sun illumination. The high conductivity and the good permeation of gel electrolyte may contribute mainly to its excellent photovoltaic performance.Graphical abstractHighlights► Dextran based hydrogel is first used to prepare quasi-solid-state polysulfide electrolyte for quantum dot-sensitized solar cells. ► The ion conductivity of hydrogel electrolyte shows almost the same value as the liquid electrolyte. ► The liquid state at elevated temperature of hydrogel electrolyte allows for a good contact between electrolyte and CdS/CdSe co-sensitized TiO2 photoanode. ► The hydrogel electrolyte based cell exhibits slightly lower power conversion efficiency than that of liquid electrolyte based cell. ► The dynamic electron transfer mechanism in hydrogel electrolyte based cell is examined in detail by EIS and CIMPS/IMVS.
Co-reporter:Lu-Yin Zhang, Yu Liu, Kang Li, Mei Pan, Cheng Yan, Shi-Chao Wei, Yong-Xin Chen and Cheng-Yong Su
CrystEngComm 2013 vol. 15(Issue 35) pp:7106-7112
Publication Date(Web):11 Jul 2013
DOI:10.1039/C3CE40845K
The reactions of pyridyl-substituted tripodal ligand 3-TPyMNTB (tris((pyridin-3-ylmethyl)benzimidazol-2-ylmethyl)amine) with Cu(II) chloride give rise to two supramolecular complexes, namely, [Cu5(3-TPyMNTB)2Cl10H2O]·6C3H7NO·11H2O (1), and [Cu5(3-TPyMNTB)2Cl8(H2O)2]Cl2·2CHCl3·2CH2OH (2). The assembly of the two complexes takes place in a stepwise route, including: (1) identical monomeric ML building units are firstly formed in both cases by the coordination of Cu(II) with 3-TPyMNTB using its four central N donors, and (2) the ML units are further linked by the 2-connecting Cu(II) ions through extending pyridyl terminals on the ligands into 0D discrete or 1D infinite structures in complexes 1 and 2, respectively. As a result, 1 presents a unique example of a M5L2 coordination cage which shows a triple helicate shape. Three Bim–Py–Cu(II)–Py–Bim coordination chains constitute the strands of the helicate, which can be outlined by an extending “molecular clip” approach, and such structural character is analyzed in detail in comparison with other known helicate examples. On the other hand, a 1D loop-and-chain structure is formed in complex 2, which can be seen as one strand of the helicate cage in complex 1 being opened up to undergo polymerization. The oxidation catalytic properties of complexes 1 and 2 are tested.
Co-reporter:Li-Lin Tan, Hong-Yan Chen, Li-Feng Hao, Yong Shen, Li-Min Xiao, Jun-Min Liu, Dai-Bin Kuang and Cheng-Yong Su
Physical Chemistry Chemical Physics 2013 vol. 15(Issue 28) pp:11909-11917
Publication Date(Web):10 May 2013
DOI:10.1039/C3CP51633D
Starburst triarylamine-based organic dyes (D1, D2, and D3) have been synthesized. For the three designed dyes, the starburst triarylamine group, thiophene (or 3,4-ethylenedioxythiophene), and cyanoacetic acid take the role of electron donor, π-conjugation bridge, and electron acceptor, respectively. These compounds are characterized by photophysical, electrochemical, and theoretical computational methods. Nanocrystalline TiO2-based dye-sensitized solar cells were fabricated using these molecules as light-harvesting sensitizers. The overall efficiencies of the sensitized cells range from 5.48 to 6.15%. It was found that the introduction of the EDOT group in D3 bathochromically extended the absorption spectra, resulting in a leap in the photovoltaic performance in comparison to D2. Incorporation of a hydrophobic carbazole-containing segment at D2 relative with D1 retarded the electron transfer from TiO2 to the oxidized dye or electrolyte, leading to an increase of electron lifetime.
Co-reporter:Guo-Bi Li, Lei Li, Jun-Min Liu, Tao Yang, and Cheng-Yong Su
Crystal Growth & Design 2013 Volume 13(Issue 4) pp:1518-1525
Publication Date(Web):March 11, 2013
DOI:10.1021/cg3017563
A unique 2-fold interpenetrated CdSO4 coordination network of the formula {[Cu2(4-pmpmd)2(CH3OH)4(opd)2]·2H2O}n [4-pmpmd = N,N′-bis(4-pyridylmethyl)phenyldiimide; opd = o-phthalic acid] has been synthesized and characterized by IR spectra, thermogravimetric (TG) analyses, elemental analyses, and single crystal and powder X-ray diffraction methods. The metal–organic framework (MOF) exhibits reversible dehydration and rehydration in a single-crystal-to-single-crystal (SC–SC) process. Moreover, the dehydrated material, having coordinatively unsaturated Cu2+ sites, can encapsulate CH3OH molecules with a color change, again in a reversible SC–SC fashion, and shows selective adsorption of CO2 over N2 and H2. This feature of obvious color variation induced by the presence of small hydroxylic molecules is highly promising for detecting hydroxylic molecules through a simple sensing mechanism. In addition, the MOF selectively interacts with hydroxylic guests and shows sorption selectivity for water, methanol, ethanol, and n-propanol over benzene guests. Notably, this compound shows complete selectivity in adsorption for n-propanol over 2-propanol owing to the effect of shape exclusion.
Co-reporter:Ying Xiong, Rui Yang, Sha Chen, Ji-Jun Jiang and Cheng-Yong Su
CrystEngComm 2013 vol. 15(Issue 45) pp:9751-9756
Publication Date(Web):06 Sep 2013
DOI:10.1039/C3CE41071D
Four non-interpenetrating 3D Ag(I) coordination polymers have been obtained from the reactions of a tripodal ligand, benzene-1,3,5-triyl triisonicotinate (BTTP4), with AgBF4, AgSbF6, AgCF3CO2 and AgCF3SO3. In all complexes, large hexagonal rings with dimensions of 16 × 19 Å (atom-to-atom separation) are formed, which share edges to fabricate the 2D honeycomb network. Parallel stacking of these honeycomb networks in an offset way sustained mainly by π–π interactions results in 2D → 3D non-interpenetrating dimension increase, affording 1D tubular ‘channels’ hosting free solvent molecules and/or counterions in the lattice. The pore size and shape are found to be influenced by the effects of counter anion, ligand conformation and π–π interactions, providing potential microporous frameworks.
Co-reporter:Qiong-Yan Yu, Jian-Feng Huang, Yong Shen, Li-Min Xiao, Jun-Min Liu, Dai-Bin Kuang and Cheng-Yong Su
RSC Advances 2013 vol. 3(Issue 42) pp:19311-19318
Publication Date(Web):06 Sep 2013
DOI:10.1039/C3RA43018A
Three new ruthenium sensitizers [Ru(H2dcbpy)(LX)(NCS)2] [H2dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine, and LX = 2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (RuLF), 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-N,N-dimethylaniline (RuLN), or 2-(4-methylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (RuLC)], have been designed and synthesized. Under standard global AM 1.5 solar conditions, the device using the RuLF sensitizer gave a conversion efficiency of 7.28%, compared to 7.50% optimized for the N719 dye. The power-conversion efficiency of RuLF is 24% and 66% higher than those of RuLN and RuLC, respectively, due to a remarkable fluoro-substitution effect. The origins of this effect have been thoroughly investigated by spectroscopic, electrochemical, and density functional theory (DFT) studies. Our results show the fluoro-substitution serves as the key factor for improving the device performance, the role of which is to increase the dye density on TiO2, alter the molecular packing, and tune the electron donating property. These findings may provide an alternative strategy for the design of a new type of ruthenium sensitizer by the introduction of C–F bonds to the auxochromic ligand to improve the device performance.
Co-reporter:Hongmiao Li, Yixuan Zhu, Jianyong Zhang, Zhenguo Chi, Liuping Chen and Cheng-Yong Su
RSC Advances 2013 vol. 3(Issue 37) pp:16340-16344
Publication Date(Web):17 Jul 2013
DOI:10.1039/C3RA40363G
To develop luminescent gels, a series of metal–organic gels have been successfully synthesised based on trivalent metal ions (Al3+, Cr3+, Fe3+, Ga3+, and In3+) and tetrakis(4-carboxyphenyl)ethylene (H4TCPE) that has aggregation-induced emission (AIE) features. Among these gels, the Al-TCPE gel has both high hierarchical micro- and mesoporosity and AIE effect. The Al-TCPE aerogel consists of metal–organic framework nanocomponents as revealed by TEM and PXRD, which contribute to its high microporosity. Using tetraphenylethylene as a building block endows the Al-TCPE gel with AIE photoluminescence. The Al-TCPE gel shows potential in the selective detection of explosives with picric acid chosen as a model explosive.
Co-reporter:Jing-An Zhang, Mei Pan, Ji-Jun Jiang, Zhi-Gang She, Zhi-Jin Fan, Cheng-Yong Su
Inorganica Chimica Acta 2013 400() pp: 1
Publication Date(Web):
DOI:10.1016/j.ica.2013.02.007
Co-reporter:Tao Yang;Hao Cui;Changhe Zhang; Li Zhang; Cheng-Yong Su
ChemCatChem 2013 Volume 5( Issue 10) pp:3131-3138
Publication Date(Web):
DOI:10.1002/cctc.201300241
Abstract
A reliable procedure for the synthesis of oxysulfonyl azides has been developed and applied to the three-component coupling reactions of azides, alkynes, and amines catalyzed homogeneously by CuI, which led to the formation of N-oxysulfonyl amidines with good yields. To fully evaluate the catalytic activity towards this coupling reaction, two coordination frameworks, namely, Cu2I2(PDIN) without micropores and Cu2I2(BTTP4) with micropores (PDIN=1,4-phenylene diisonicotinate, BTTP4=benzene-1,3,5-triyltriisonicotinate), were prepared by a facile one-pot reaction as heterogeneous catalysts. Catalytic results showed that nonporous Cu2I2(PDIN) was almost inactive for the three-component coupling reaction, whereas microporous Cu2I2(BTTP4) was an efficient heterogeneous catalyst for the synthesis of N-oxysulfonyl amidines. Furthermore, porous Cu2I2(BTTP4) displayed a shape-selective performance with respect to the alkyne substrates, and aromatic alkynes were preferable to aliphatic alkynes. The location of the catalytically active sites in the Cu2I2(BTTP4) framework has been studied by a series physical techniques, which includes powder XRD, CO2 gas adsorption, IR spectroscopy, energy dispersive X-ray analysis, and X-ray photoelectron spectroscopy, which suggests that the catalytic sites are not only on the external surface but also inside the micropores.
Co-reporter:Xiting Zhang, Zhuofeng Ke, Nathan J. DeYonker, Huiying Xu, Zhi-Feng Li, Xianyan Xu, Xuepeng Zhang, Cheng-Yong Su, David Lee Phillips, and Cunyuan Zhao
The Journal of Organic Chemistry 2013 Volume 78(Issue 24) pp:12460-12468
Publication Date(Web):November 26, 2013
DOI:10.1021/jo402101h
The mechanisms and enantioselectivities of the dirhodium (Rh2L4, L = formate, N-methylformamide, S-nap)-catalyzed intramolecular C–H aminations of 3-phenylpropylsulfamate ester have been investigated in detail with BPW91 density functional theory computations. The reactions catalyzed by the Rh2II,II catalysts start from the oxidation of the Rh2II,II dimer to a triplet mixed-valent Rh2II,III–nitrene radical, which should facilitate radical H-atom abstraction. However, in the Rh2(formate)4-promoted reaction, as a result of a minimum-energy crossing point (MECP) between the singlet and triplet profiles, a direct C–H bond insertion is postulated. The Rh2(N-methylformamide)4 reaction exhibits quite different mechanistic characteristics, taking place via a two-step process involving (i) intramolecular H-abstraction on the triplet profile to generate a diradical intermediate and (ii) C–N formation by intersystem crossing from the triplet state to the open-shell singlet state. The stepwise mechanism was found to hold also in the reaction of 3-phenylpropylsulfamate ester catalyzed by Rh2(S-nap)4. Furthermore, the diradical intermediate also constitutes the starting point for competition steps involving enantioselectivity, which is determined by the C–N formation open-shell singlet transition state. This mechanistic proposal is supported by the calculated enantiomeric excess (94.2% ee) with the absolute stereochemistry of the product as R, in good agreement with the experimental results (92.0% ee).
Co-reporter:Yu Liu, Mei Pan, Qing-Yuan Yang, Lei Fu, Kang Li, Shi-Chao Wei, and Cheng-Yong Su
Chemistry of Materials 2012 Volume 24(Issue 10) pp:1954
Publication Date(Web):April 30, 2012
DOI:10.1021/cm3008254
A new bifunctional NTB (tris(benzimidazol-2-ylmethyl)amine)-type ligand incorporating coordination discriminable tripodal benzimidazolyl and monodentate pyridyl groups, tris((pyridin-3-ylmethyl)benzoimidazol-2-ylmethyl)amine (3-TPyMNTB), has been prepared to assemble 4d–4f heterometallic three-dimensional metal–organic frameworks (MOFs) in a stepwise route: (1) direct reaction of 3-TPyMNTB with Ln(ClO4)3 affords monomeric complexes [Eu(3-TPyMNTB)2](ClO4)3·2.5MeCN (1-Eu) and [Gd(3-TPyMNTB)2](ClO4)3·2MeCN·2CHCl3 (1-Gd), and (2) assembly of the precursors 1-Eu and 1-Gd with AgClO4 gives rise to infinite MOFs [EuAg3(3-TPyMNTB)2(H2O)(MeCN)](ClO4)6·4MeCN (2-Eu-Ag) and [GdAg3(3-TPyMNTB)2(H2O)(MeCN)](ClO4)6·4MeCN (2-Gd-Ag), respectively. In monomer 1-Eu, the ligand shows an antenna effect to transfer absorbed energy to Eu3+ center to emit characteristic red luminescence, while in 4d–4f heterometallic MOF 2-Eu-Ag, the ligand centered emission is resensitized by Ag+ ions to generate dual emissions, coming up with the direct white-light emission from a single crystal. The detailed photoluminescent study has been carried out in both solid state and solution to elucidate the emission nature.Keywords: europium; metal−organic framework; photoluminescence; silver; white-light emission;
Co-reporter:Cheng Yan, Kang Li, Shi-Chao Wei, Hai-Ping Wang, Lei Fu, Mei Pan and Cheng-Yong Su
Journal of Materials Chemistry A 2012 vol. 22(Issue 19) pp:9846-9852
Publication Date(Web):13 Apr 2012
DOI:10.1039/C2JM00001F
In this paper, we report the design of a new functionalized tripodal ligand triCB-NTB (4,4′,4′′-(2,2′,2′′-nitrilotris(methylene)tris(1H-benzo[d]imidazole-2,1-diyl)tris(methylene))tribenzoic acid) and its assembly of Eu(III) homometallic or Zn(II)-Eu(III) heterometallic lanthanide-based metal–organic frameworks (MOFs). C3 symmetric Eu(III) center is achieved in the homometallic MOF, [Eu(triCB-NTB)]·DMAc·4H2O (1). The C3 axis of the three coordinated imino N atoms on the propeller-extended central triCB-NTB ligand coincides with the C3 axis that directs the three para-methyl carboxylic benzene arms on three surrounding ligands coordinating with the central Eu(III) simultaneously. Therefore, a (6, 3) pattern is formed in the framework with relatively large porosity. In the Zn-Eu heterometallic framework, [EuZn(triCB-NTB)(H2O)(Cl)2]·2DMAc·H2O (2), the N atoms on the triCB-NTB are coordinated with Zn(II) and the carboxylic O atoms are coordinated with Eu(III). A paddle-wheel linked Eu(III)2 cluster is formed and 1D loop-and-chain structure is obtained. Two ligands, two Zn(II) ions and two Eu(III)2 clusters constitute one box-like unit on the loop chain. Due to the non-inversion symmetry imposed on the central Eu(III) and the large polarizability of the ligand, both one photon (OP) luminescence based on the energy transfer from the ligand to Eu3+ and two photon (TP) luminescence based on the hypersensitive transition of the Eu3+ ions are observed in the two lanthanide-based MOFs. This satisfies the urgent needs of multi-mode luminescent lanthanide complex. Simultaneously, N2 gas and selective vapor adsorptions were also detected in the porous structure of complexes 1 and 2 due to their benzene-filled channels. The six-pointed-star like cavities in 1 can let the gas and vapor molecules go in and out smoothly subject to changes in the pressure, while the narrower and more irregular channels in 2 show irreversible adsorption behavior for benzene and cyclohexane vapor molecules in vacuum under room temperature.
Co-reporter:Hong-Yan Chen, Dai-Bin Kuang and Cheng-Yong Su
Journal of Materials Chemistry A 2012 vol. 22(Issue 31) pp:15475-15489
Publication Date(Web):28 May 2012
DOI:10.1039/C2JM32402D
As one of the most promising low cost alternatives to the traditional p–n junction photovoltaic device, the dye-sensitized solar cell (DSSC) has attracted immense attention from academic and industrial researchers in the last two decades. The size, structure and morphology of photoanode materials have been found to show significant influence on the photovoltaic performance of DSSCs. In this feature article, we briefly summarize the synthesis and properties of hierarchically micro/nanostructured semiconductor (TiO2, ZnO, SnO2) photoanode materials involving microspheres and one-dimensional nanostructure, and their photovoltaic performance in DSSCs.
Co-reporter:Lei Fu, Mei Pan, Yan-Hu Li, Hong-Bin Wu, Hai-Ping Wang, Cheng Yan, Kang Li, Shi-Chao Wei, Zi Wang and Cheng-Yong Su
Journal of Materials Chemistry A 2012 vol. 22(Issue 42) pp:22496-22500
Publication Date(Web):04 Sep 2012
DOI:10.1039/C2JM34992B
A novel butterfly-like Ir(III) complex is designed, synthesized, and characterized for highly efficient yellow phosphorescent polymer-based light-emitting diodes (PLEDs). The device shows a maximum external quantum efficiency of 19.2%, luminance efficiency of 40 cd A−1 and Commission International de L'Eclairage (CIE) color coordinates of (0.49, 0.50) at J = 1.2 mA cm−2.
Co-reporter:Guo-Bi Li, Jian-Rong He, Jun-Min Liu and Cheng-Yong Su
CrystEngComm 2012 vol. 14(Issue 6) pp:2152-2158
Publication Date(Web):17 Jan 2012
DOI:10.1039/C2CE06147C
Three new zinc coordination polymers, namely {[Zn(4-pmntd)Cl2]·H2O}n (1), {[Zn(4-pmntd)(CH3CN)4]·(ClO4)2·H2O}n (2), and {[Zn(4-pmntd)(H2O)4]·(CF3SO3)2·3H2O}n (3) (4-pmntd = N,N′-bis(4-pyridylmethyl)-naphthalene diimide) have been synthesized by reactions of 4-pmntd with ZnCl2, Zn(ClO4)2, and Zn(CF3SO3)2, respectively. Compound 1 is an unusual one-dimensional (1D) single-stranded double helical chain containing tubular channels; 2 is an uncommon 1D zigzag chain arranged in a cross-like fashion to generate a 3D plywood-like array; 3 is a typical 1D zigzag chain arranged in a parallel array containing 1D quadrangle channels to accommodate the counter anions and water molecules. The structural diversity in these compounds is attributed to different coordination abilities, sizes, and geometries of counter anions. The anion exchange property of 3 was investigated.
Co-reporter:Xiao-Ming Lin, Ting-Ting Li, Lian-Fen Chen, Li Zhang and Cheng-Yong Su
Dalton Transactions 2012 vol. 41(Issue 34) pp:10422-10429
Publication Date(Web):18 Jun 2012
DOI:10.1039/C2DT30935A
A microporous Pb(II) metal–organic framework (MOF) [PbL2]·2DMF·6H2O (1) has been assembled from a N-oxide and amide doubly functionalized ligand HL (= N-(4-carboxyphenyl)isonicotinamide 1-oxide). Complex 1 features a three-dimensional (3D) framework possessing one-dimensional (1D) rhombic channels with dimensions of 13 × 13 Å2. The 3D framework is built up from 1D PbO2 chains that link ligands in parallel fashion to construct single-wall channels. When recrystallizing 1 in a DMSO–DMF mixture (3:5 v/v), a new coordination polymer, [PbL2]·DMF·2H2O (2), was obtained. Complex 2 is also a 3D framework containing 1D rectangular channels, but the channel dimensions become reduced in size to 13 × 8 Å2 due to reorganization of the Pb(II) coordination environment. The PbO2 chains in 2 are reformed to link ligands in a double-wall fashion, significantly reducing the channel size. Even though, the guest exchange study indicates that the DMF molecules in 2 could be replaced with benzene molecules when immersing in benzene solvent, showing single-crystal-to-single-crystal (SC–SC) guest exchange in the solid state and leading to a daughter crystal [PbL2]·0.5C6H6·2H2O (2′). Desolvated 1 and 2 display preferential adsorption behaviors of water vapour over CO2 due to the hydrophilic nature of the channels and the strong host–guest interactions. Catalytic tests indicate that desolvated 1 and 2 have size-selective catalytic activity towards the Knoevenagel condensation reaction.
Co-reporter:Kang Li, Yu Liu, Cheng Yan, Lei Fu, Shi-Chao Wei, Hai-Ping Wang, Mei Pan and Cheng-Yong Su
CrystEngComm 2012 vol. 14(Issue 11) pp:3868-3874
Publication Date(Web):13 Apr 2012
DOI:10.1039/C2CE06605J
In this paper, we report the design and synthesis of two pyridyl-substituted tripodal ligands, 3-TPyMNTB (tris(((pyridin-3-ylmethyl)benzimidazol-2-yl)methyl)amine) and 4-TPyMNTB (tris(((pyridin-4-ylmethyl)benzimidazol-2-yl)methyl)amine). Reaction of these two ligands with Eu(III)/Tb(III) picrate salts gives mononuclear complexes [Eu(3-TPyMNTB)(pic)3]·2H2O (1) and [Tb(3-TPyMNTB)(pic)3]·2H2O (2), respectively. While reaction with Eu(III)/Tb(III) nitrate salts leads to cocrystallization of a coordinative motif and an inorganic salt in one single-crystal, namely, [Eu(3-TPyMNTB)(NO3)3]·0.5[Eu(NO3)3(H2O)4]·3CH3CN (3), [Tb(3-TPyMNTB)(NO3)3]·0.5[Tb(NO3)3(H2O)4]·3CH3CN·1.5C2H5OH (4), [Eu(4-TPyMNTB)(NO3)3]·[Eu(NO3)3(H2O)3]·3CH3CN·0.5H2O (5) and [Tb(4-TPyMNTB)(NO3)3]·[Tb(NO3)3(H2O)3]·3CH3CN·0.5H2O (6). In these cocrystals, the organic ligand-coordinated motif [Ln(3(4)-TPyMNTB)(NO3)3] and the nitrate anion-bonded motif [Ln(NO3)3(H2O)n] (Ln = Eu(III) or Tb(III), n = 3 or 4) provide two Eu(III)/Tb(III) centers which coexist in the same crystal lattice. Of most interest, both coordinative and inorganic centers can be excited by the absorption of the organic ligand, that is, the double luminescent centers in the cocrystalline systems can be sensitized by the same antenna source. Therefore, both Dexter and Förster mechanisms are proposed to be involved in the emission process, in which the energy transfer is conducted either through direct bond linkages or through space from unlinked organic antennae.
Co-reporter:Guo-Bi Li, Jian-Rong He, Mei Pan, Hai-Ying Deng, Jun-Min Liu and Cheng-Yong Su
Dalton Transactions 2012 vol. 41(Issue 15) pp:4626-4633
Publication Date(Web):29 Feb 2012
DOI:10.1039/C2DT11815G
Four semirigid ditopic ligands, N,N′-bis(3-pyridylmethyl)-pyromellitic diimide (L11), N,N′-bis(4-pyridylmethyl)-pyromellitic diimide (L22), N,N′-bis(3-pyridylmethyl)-naphthalene diimide (L33), and N,N′-bis(4-pyridylmethyl)-naphthalene diimide (L44), reacted with Cd(NO3)2 to result in four cadmium(II) complexes, namely, {[Cd2(L11)2(NO3)4(CH3OH)4]·H2O} (1), [Cd(L22)(NO3)2(CH3OH)2·Cd2(L22)3(NO3)4]·{4(HCCl3)·2H2O}n (2), {[Cd(L33)2(NO3)2]}n (3), and {[Cd(L44)2(NO3)2]·2(CHCl3)}n (4). These complexes have been characterized by elemental analyses, powder X-ray diffraction, thermogravimetric (TG) analyses, IR spectroscopy, and single-crystal X-ray diffraction. Structural analyses show that four types of structures are formed: (1) a discrete M2L2 ring with two Cd ions and two cis-L11 ligands comprising a zero-dimensional molecular rectangle (0D), (2) an unusual zigzag linear chain and a one-dimensional ladder existing simultaneously in the crystal lattice (1D), (3) a two-dimensional network of the (4,4) net structure (2D), and (4) an unusual chiral three-dimensional framework with 5-fold interpenetrating diamond (dia) topology (3D). In these complexes, the ligands exhibit different coordination modes and construct various architectures by bridging Cd(NO3)2 inorganic building blocks. These results suggest that structural diversity of the complexes is tunable by ligand modifications, that is, varying the ligand spacer bulkiness or substituent position of terminal group. Furthermore, gas adsorption measurements indicate that 4 possesses moderate CO2 uptake and some adsorption selectivity for CO2 over N2.
Co-reporter:Zhi-Quan Yu, Mei Pan, Ji-Jun Jiang, Zhi-Min Liu, and Cheng-Yong Su
Crystal Growth & Design 2012 Volume 12(Issue 5) pp:2389-2396
Publication Date(Web):March 23, 2012
DOI:10.1021/cg300051w
Reaction of a balance-like dipodal ligand 2,6-bis(pyridiyl) hexahydro-4,8-ethenopyrrolo [3,4-f]isoindole-1,3,5,7-tetrone (3-pybtd) with various Cd(II) salts afforded eight complexes, namely, [Cd2(3-pybtd)2(NO3)4(C2H5OH)2(H2O)2] (1), [Cd2(3-pybtd)2(SiF6)2(DMF)4(H2O)2](H2O)4·(DMF)2 (2), {[Cd(3-pybtd)2(H2O)4](ClO4)2}n (3), {[Cd(3-pybtd)2(OTf)2]·THF}n (4), {[Cd(3-pybtd)2(SCN)2]·(H2O)2}n (5), [Cd(3-pybtd)(OTs)2(DMF)2]n (6), [Cd(3-pybtd)2(OTs)2]n (7), and {[Cd2(3-pybtd)2Cl10/3][CdCl8/3]·(H2O)3}n (8). Complexes 1 and 2 are zero-dimensional (0D) square-like or olive-like dimeric M2L2 metallacycles, showing a pair of shape-modified molecular rectangles due to different conformations of the ligands and coordination orientation of the metal centers. Complexes 3–5 are one-dimensional (1D) looplike chains composed of olive-like M2L2 metallacycle building units as in 2, showing 0D → 1D dimension increase via ligand addition, while complex 8 is a three-dimensional (3D) framework retaining the same olive-like M2L2 metallacycle, showing 0D → 3D dimension increase via linkage of μ3-Cl bridged Cd(II) clusters. Complex 6 is a wave-like MnLn chain, possessing the same ML building units as in 1 but showing 0D → 1D dimension increase via ring-opening polymerization. Replacement of DMF molecules from the coordination sphere in 6 by the ligands resulted in a two-dimensional (2D) (4, 4) network of 7, showing 1D → 2D dimension increase from 6 via ligand addition or 1D → 2D dimension increase from 3–5 via ring-opening polymerization. Complexes 3–5 also represent a series of supramolecular isomorphs displaying anion exchange properties. Electrospray ionization mass spectrometry (ESI-MS) studies in solution suggest that the discrete and infinite structures in 1, 6, and 7 are assembled from the same monomeric ML building blocks, which crystallize in a different way to lead to structural diversification via dimerization or polymerization during the crystallization.
Co-reporter:Shao-Yong Li, Yao-Wei Xu, She-Quan Zeng, Li-Min Xiao, Hong-Quan Duan, Xue-Lian Lin, Jun-Min Liu, Cheng-Yong Su
Tetrahedron Letters 2012 Volume 53(Issue 23) pp:2918-2921
Publication Date(Web):6 June 2012
DOI:10.1016/j.tetlet.2012.04.003
A fluorescent chemosensor based on a calix[4]arene derivative conjugated with four thiophene-cyanoarylic acid groups at the upper rim displays high selectivity toward acidic amino acids in pure aqueous media through multiple H-bond interactions. The interactions of Asp/Glu with the chemosensor have been investigated by fluorescence and UV–Vis titrations, ESI-MS assay, 1H NMR spectra, and molecular modeling method.
Co-reporter:Qiong-Yan Yu, Bing-Xin Lei, Jun-Min Liu, Yong Shen, Li-Min Xiao, Rong-Liang Qiu, Dai-Bin Kuang, Cheng-Yong Su
Inorganica Chimica Acta 2012 Volume 392() pp:388-395
Publication Date(Web):30 September 2012
DOI:10.1016/j.ica.2012.03.047
Three heteroleptic pyridine/benzimidazole-based ruthenium sensitizers, [Ru(L1)(dcbpyH2)NCS](SCN) (Y1, L1 = 2,6-bis(1-benzylbenzimidazol-2-yl)-pyridine, dcbpyH2 = 4,4′-dicarboxylic acid-2,2′-bipyridine), [Ru(L2)(dcbpyH2)NCS](SCN) (Y2, L2 = 2,6-bis(1-ethylbenzimidazol-2-yl)-pyridine), and [Ru(L3)(dcbpyH2)NCS](SCN) (Y3, L3 = 2,6-bis(1-hexylbenzimidazol-2-yl)-pyridine) are synthesized and applied to dye-sensitized solar cells (DSSCs). The power-conversion efficiency of dye Y3 is higher than those of dyes Y1 and Y2, due to the modification of the auxochromic ligand with a hexyl moiety. The origins of the performance diversity in these devices have been studied with respect to power-conversion efficiency by UV–Vis absorption and emission spectra, cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), intensity modulated photocurrent spectroscopy (IMPS), intensity modulated photovoltage spectroscopy (IMVS), and density functional theory (DFT) studies. The better solar-cell performance of Y3 compared to Y1 and Y2 was believed to derive from the enhanced electron lifetimes.Graphical abstractThree heteroleptic pyridine/benzimidazole-based ruthenium sensitizers have been synthesized and the influence of the benzimidazole substituents on the device performance in dye-sensitized solar has been studied. We found that the hexyl-substituted Y3 had a higher power conversion efficiency than those on phenyl-substituted Y1 and ethyl-substituted Y2, because the hexyl-substituted dye gave higher electron collection efficiency and availably retarded charge recombination.Highlights► Three novel heteroleptic pyridine/benzimidazole-based ruthenium sensitizers. ► The benzimidazole substituents influence the device performance in DSSCs. ► The performance differences of three dyes are analyzed by electrochemical data.
Co-reporter:Hai-Ping Wang, Shi-Chao Wei, Mei Pan, Kang Li, Zi Wang, Cheng Yan, Cheng-Yong Su
Inorganic Chemistry Communications 2012 Volume 25() pp:48-50
Publication Date(Web):November 2012
DOI:10.1016/j.inoche.2012.09.010
A pentadentate ligand L (2-(2-((bis(pyridin-2-ylmethyl)amino)methyl)phenoxy) -N,N-diphenylacetamide) was self-assembled with Eu (NO3)3 or Zn (NO3)2/Eu (NO3)3 to give homometallic complex ([EuL(NO3)3], 1) or ion associating complex ([ZnL(NO3)]2·[Eu(NO3)5]·CH3CN, 2), respectively. The photoluminescent behavior and energy transfer process were studied in the two complexes by excitation in different ways, in which 2 shows Förster energy transfer mechanism.Förster energy transfer can happen in Eu–Zn ion associating complex.Highlights► Using the same pentadentate ligand, homometallic Eu and ion associating Eu–Zn complexes are obtained. ► Förster energy transfer can happen in Eu–Zn ion associating complex.
Co-reporter:Qiu-Ping Luo, Xiao-Yun Yu, Bing-Xin Lei, Hong-Yan Chen, Dai-Bin Kuang, and Cheng-Yong Su
The Journal of Physical Chemistry C 2012 Volume 116(Issue 14) pp:8111-8117
Publication Date(Web):March 16, 2012
DOI:10.1021/jp2113329
The reduced graphene oxide (RGO)-hierarchical ZnO hollow sphere composites are prepared through a simple ultrasonic treatment of the solution containing graphene oxide (GO), Zn(CH3COO)2, DMSO, and H2O. The GO is reduced to RGO effectively, and the ZnO hollow spheres consisting of nanoparticles are uniformly dispersed on the surface of RGO sheets during the ultrasonic process. The optimum synergetic effect of RGO-ZnO composites is found at a RGO mass ratio of 3.56%, and the photocurrent and photodegradation efficiency on methylene blue of RGO-ZnO composites are improved by five times and 67%, respectively, compared with those of pure ZnO hollow spheres. The enhancements of photocurrent and photocatalytic activity can be attributed to the suppression of charge carriers recombination resulting from the interaction between ZnO and RGO.
Co-reporter:Mei Pan, Xiao-Ming Lin, Guo-Bi Li, Cheng-Yong Su
Coordination Chemistry Reviews 2011 Volume 255(15–16) pp:1921-1936
Publication Date(Web):August 2011
DOI:10.1016/j.ccr.2011.03.013
1,4,5,8-naphthalenediimide (NDI) derivatives are versatile in coordination and material chemistry due to their large conjugated planar structure and special electron transfer properties. This review presents an overview of metal–organic materials derived from NDIs with their structural models, analytical techniques and potential applications outlined.Graphical abstract. A short summary of the metal–organic materials based on 1,4,5,8-naphthalenediimides (NDIs) is presented with respect to their structural models, analytical techniques and potential applications.Highlights► NDIs show versatile conformational and electronic structures. ► Metal–organic materials based on NDIs show diversified structures and applications. ► Various analytical techniques have been applied in the study of the NDIs systems.
Co-reporter:Sujuan Wang, Lei Li, Jianyong Zhang, Xiaochen Yuan and Cheng-Yong Su
Journal of Materials Chemistry A 2011 vol. 21(Issue 20) pp:7098-7104
Publication Date(Web):31 Mar 2011
DOI:10.1039/C1JM10394F
A structurally flexible porous metal–organic framework, [CuII(bped)2(H2O)2(SiF6)] ⊃ 4H2O (Cu-MOF-SiF6) was prepared from CuSiF6 and meso-1,2-bis(4-pyridyl)-1,2-ethanediol (bped) in EtOH–H2O. Cu-MOF-SiF6 is a three-dimensional (3D) polycatenated framework consisting of two-dimensional (2D) (4,4) topological grid networks which display 2-fold inclined interpenetration in the crystal lattice. The SiF62− anions hosted in the one-dimensional channels of Cu-MOF-SiF6 can be readily exchanged with NO3− anions while keeping the framework intact, leading to isomorphous Cu-MOF-NO3. The Cu-MOFs show selective adsorption behaviors due to the host–guest interaction, which is dependent on the anions and the guest size. The MeOH uptake investigation indicates that Cu-MOF-SiF6 demonstrates a breathing effect, while Cu-MOF-NO3 exhibits distinctive stepwise MeOH sorption due to the smaller size of NO3− and the larger voids in the crystal lattice. Cu-MOF-NO3 also exhibits stepwise sorption for larger EtOH guests, while the uptake of EtOH is blocked in Cu-MOF-SiF6. In addition, the solids show anion-responsive catalytic properties. Both Cu-MOF-SiF6 and Cu-MOF-NO3 efficiently oxidize benzylic compounds to the corresponding carbonyl functionality under mild and convenient reaction conditions, but improved catalytic activity was observed for Cu-MOF-NO3. The catalysts can be reused with the framework left intact at least three times without losing of any activity.
Co-reporter:Qiu-Ping Luo, Bing-Xin Lei, Xiao-Yun Yu, Dai-Bin Kuang and Cheng-Yong Su
Journal of Materials Chemistry A 2011 vol. 21(Issue 24) pp:8709-8714
Publication Date(Web):10 May 2011
DOI:10.1039/C1JM10871A
Vertically aligned hierarchical ZnO rod-in-tube nano-architecture arrays are produced via a two-step process including an initial hydrothermal reaction followed by ultrasonication growth. The ZnO nanorod arrays grow firstly on FTO glass through a hydrothermal process and then act as templates for the fabrication of rod-in-tube nano-architectures during ultrasonication. The as-prepared ZnO rod-in-tube nano-architectures are assembled by the self-stacking of hexagonal nanorings along with <001> orientation of ZnO nanorod templates. Both hexamethylenetetramine and sodium citrate are found to play key roles in the formation of the novel ZnO rod-in-tube nano-architectures. The power conversion efficiency of dye-sensitized solar cell based on hierarchical ZnO rod-in-tube nano-architectures photoelectrode (0.91%) exhibits a significant improvement (75%) compared to that of ZnO nanorods (0.52%).
Co-reporter:Qing-Yuan Yang, Kang Li, Jian Luo, Mei Pan and Cheng-Yong Su
Chemical Communications 2011 vol. 47(Issue 14) pp:4234-4236
Publication Date(Web):25 Feb 2011
DOI:10.1039/C0CC05464J
Reaction of a semi-rigid tripodal ligand 1,1′,1′′-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)tripyridinium-4-olate) (TTP) with Ln3+ (Ln = Eu, Gd) afforded rare (3,12)-connected metal–organic frameworks (MOFs). A topological simplification of such highly connected 3D MOFs on the basis of 2D CdI2 (3,6)-nets is proposed. The luminescent and anion exchange properties of the compounds were determined.
Co-reporter:Xiaobing Wang, Jing Huang, Shenglin Xiang, Yu Liu, Jianyong Zhang, Andreas Eichhöfer, Dieter Fenske, Shi Bai and Cheng-Yong Su
Chemical Communications 2011 vol. 47(Issue 13) pp:3849-3851
Publication Date(Web):14 Feb 2011
DOI:10.1039/C0CC05235C
Ag6L6-type coordination nanotubular structures have been assembled from 6 Ag(I) ions and 6 T-shaped ligands, 4-(3,5-bis(diphenylphosphino)phenyl)pyridine; the nanotubes represent a discrete molecular architecture of a number of polymeric structures assembled from dimeric building blocks.
Co-reporter:Guo-Bi Li, Jun-Min Liu, Yue-Peng Cai, and Cheng-Yong Su
Crystal Growth & Design 2011 Volume 11(Issue 7) pp:2763
Publication Date(Web):May 31, 2011
DOI:10.1021/cg1014913
A series of Mn(II), Cd(II), and Co(II) metal–organic frameworks, namely, {[Mn(L1)(NCS)2(CH3OH)2]·2(CH3OH)}n (1), {[Mn(L2)2(NCS)2(CH3OH)2]}n (2), {[Mn(L3)2(NCS)2]·0.5(CH3OH)·4.5H2O}n (3), {[Cd(L1)(I)2]·3(H2O)}n (4), {[Cd(L2)(I)2]}n (5), {[Cd(L3)(NCS)2]·2.5(H2O)}n (6), {[Co(L1)2(NCS)2]·4(H2O)}n (7), {[Co(L2)2(NCS)2]·(HCCl3) }n (8), and {[Co(L3)2(NCS)2]·3(H2O)}n (9) (where L1 = N,N′-bis(4-pyridylmethyl)-pyromellitic diimide, L2 = N,N′-bis(3-pyridylmethyl)-pyromellitic diimide, L3 = N,N′-bis(4-pyridylmethyl)-naphthalene diimide), were synthesized and structurally characterized by elemental analyses, thermogravimetric (TG) analyses, powder X-ray diffraction, IR spectroscopy, and single-crystal X-ray diffraction. In Mn(II) complexes 1–3, L1 connects the adjacent metal centers to form an infinite one-dimensional (1D) zigzag coordination polymeric chain, L2 acts as a monodentate ligand to give mononuclear coordination motifs, while L3 bridges two metal ions to generate two-dimensional (2D) networks of the (4, 4) net topology containing rhombic grids. In Cd(II) complexes 4–6, L1, L2, and L3 act as bidentate ligands and coordinate with two metal ions to form three different coordination polymers that display diversified structures, that is, infinite 1D zigzag chain in 4, single-stranded double helical chain in 5, and 2D networks of the (4, 4) net in 6. For three Co(II) complexes, 7 is a three-dimensional (3D) framework with 3-fold interpenetrating dia topology, while 8 and 9 have similar two-dimensional (2D) networks of the (4, 4) net topology. The results show that the conformation and coordination mode of organic ligands and the coordination geometry of metal centers play important roles in determining the structure and topology of the complexes. Furthermore, the gas sorption properties were measured, and complex 7 shows a highly selective sorption behavior toward CO2, which can be a promising candidate as adsorbents for CO2/N2 separation. In addition, the luminescence properties of 5–6 were studied in the solid state at room temperature.
Co-reporter:Yu Liu, Mei Pan, Kang Li, Cheng Yan, Yong Shen, Cun-Yuan Zhao, Wei Wang, and Cheng-Yong Su
Crystal Growth & Design 2011 Volume 11(Issue 11) pp:4876-4884
Publication Date(Web):September 8, 2011
DOI:10.1021/cg200701j
To explore the influencing effect of different transition metal ions on the coordination geometries and structural architectures of metal–organic complexes with the same ligand, 10 new coordination compounds of a monobranched tripodal ligand N-[N′-(carboxymethyl)benzimidazol-2-ylmethyl]-N,N-bis(benzimidazol-2-ylmethyl)amine (HAcNTB), namely, [Co6(AcNTB)6]·6ClO4·36H2O (Co-ClO4), [Co6(AcNTB)6]·6BF4·9H2O·3CHCl3 (Co-BF4), [Zn6(AcNTB)6]·6ClO4·2CHCl3·15H2O (Zn-ClO4), [Zn6(AcNTB)6]·6BF4·52H2O (Zn-BF4), [Ni2(AcNTB)2(H2O)2]·2ClO4·2CH3OH·2H2O (Ni-ClO4), [Ni2(AcNTB)2(H2O)2]·2BF4·4CH3OH (Ni-BF4), {[Mn(AcNTB)(CH3OH)]·ClO4·H2O}n (Mn-ClO4), {[Mn(AcNTB)(CH3OH)]·BF4·H2O}n (Mn-BF4), {[Cd(AcNTB)(CH3OH)]·ClO4·H2O}n] (Cd-ClO4), {[Cd(AcNTB)(CH3OH)]·BF4·H2O}n (Cd-BF4) have been synthesized and characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. In isomorphous complexes Co-ClO4, Co-BF4, Zn-ClO4, and Zn-BF4, the metal centers (Zn2+ and Co2+) are five-coordinated in a trigonal bipyramid geometry, leading to formation of hexameric rings through linkage of six metals and six ligands without coordination of anion and solvent molecules. In isomorphous complexes Ni-ClO4 and Ni-BF4, the metal centers (Ni2+) prefer a six-coordinated octahedral geometry, resulting in dinuclear rings through connection of two metals and two ligands with water molecule participating in coordination. While in the isomorphous complexes Mn-ClO4, Mn-BF4, Cd-ClO4, and Cd-BF4, the metal centers are seven-coordinated to form one-dimensional (1D) chain, showing an irregularly distorted geometry with water or methanol solvents entering coordination sphere. The coordination geometric preference of different metal ions with respect to the metal ionic radii and coordination numbers play an important role in determining the assembly fashions. Density functional theory (DFT) calculations have been performed to track the stability effects obtained by the metal ions in different coordination environments.
Co-reporter:Yu Liu, Kang Li, Shi-Chao Wei, Mei Pan and Cheng-Yong Su
CrystEngComm 2011 vol. 13(Issue 14) pp:4564-4571
Publication Date(Web):17 May 2011
DOI:10.1039/C1CE05210A
Reactions of the mono-branched tripodal ligand, N-[N′-(carboxymethyl)benzimidazol-2-ylmethyl]-N,N-bis(benzimidazol-2-ylmethyl)amine (HAcNTB), with different Cu2+ salts under varied conditions have resulted in six new Cu2+ coordination assemblies, namely, [Cu6(AcNTB)6](BF4)6·30H2O (1-BF44), [Cu3(AcNTB)3](SiF6)1.5·CH3CN·CH3OH·8H2O (2-SiF66), [Cu(AcNTB)](CH3C6H4SO3)·CH3OH (3-OTs), [Cu(AcNTB)](ClO4)·0.5C6H5NO2·2.5H2O (3-ClO44-PhNO22), [Cu(AcNTB)](NO3)·0.5C6H5NO2·4.25H2O (3-NO33-PhNO22) and [Cu2(AcNTB)2](NO3)2·0.5CH3C6H5·2CH3OH·H2O (3-NO33-MePh). The common feature of these complexes is that, similar chiral [Cu(AcNTB)]+ building blocks are formed with three arms of the tripodal ligand wrapping around the Cu2+ centers in either clockwise (Δ-conformer) or anticlockwise (Λ-conformer) fashion, and such building blocks are further assembled with the carboxylate branch (Ac group) acting as bridge by forming Cu–O coordination bond. As a consequence, the assembly process is controlled by the bridging fashion of Ac group between the [Cu(AcNTB)]+ building blocks. In complex 1-BF44 three Δ-conformers and three Λ-conformers are alternately connected to form a cyclic meso-hexamer, in complex 2-SiF66 three Δ-conformers (or three Λ-conformers) are connected to form discrete chiral-trimers (ΔΔΔ-trimer or ΛΛΛ-trimer), while in complexes 3-OTs, 3-ClO44-PhNO22, 3-NO33-PhNO22 and 3-NO33-MePh the same handed conformers are connected into one-dimensional (1D) chiral-chains (ΔΔΔ-chain or ΛΛΛ-chain). Structural analyses disclose that the assembly fashion and chirality transfer in theses complexes are modulated by the supramolecular interactions including N–H⋯F hydrogen bonds, intra- and inter-molecular π–π interactions which are directed by the counter anions as well as additional aromatic molecules.
Co-reporter:Kumar Biradha, Cheng-Yong Su, and Jagadese J. Vittal
Crystal Growth & Design 2011 Volume 11(Issue 4) pp:875-886
Publication Date(Web):February 24, 2011
DOI:10.1021/cg101241x
In recent years, Asian countries, especially China and India, are making significant progress in the field of crystal engineering. The recent surge of publications in this area from these countries in high impact journals is a tangible measure of this activity. An important milestone in this direction was the China−India−Singapore Symposium on Crystal Engineering recently held at the National University of Singapore. This symposium brought researchers working in this field to meet, discuss, present, and exchange their research work and has generated momentum to further accelerate the growth of this field. This perspective highlights the recent advances discussed by the researchers at this symposium in the fast growing field of crystal engineering.
Co-reporter:Jing-An Zhang, Mei Pan, Ji-Jun Jiang, Zhi-Gang She, Zhi-Jin Fan, Cheng-Yong Su
Inorganica Chimica Acta 2011 Volume 374(Issue 1) pp:269-277
Publication Date(Web):1 August 2011
DOI:10.1016/j.ica.2011.02.073
Eleven transition metal complexes of three asymmetrical tridentate thioether ligands, 8-((pyridin-2-yl)methylthio) quinoline (TQMP2), 8-((pyridin-3-yl)methylthio) quinoline (TQMP3), 8-((pyridin-4-yl)methylthio) quinoline (TQMP4) and one symmetrical pentadentate ligand 2,6-bis (8-quinolinylthiomethyl) pyridine (DTQMP) were prepared. The structures of all these complexes were identified by means of elemental analysis (EA), infrared spectra (IR) and single-crystal diffraction, providing three different kinds of basic conformations, (1) discrete mononuclear structures, (2) dinuclear rings and (3) 1D polymer chains. The antibacterial, antifungal and pesticide activities of the four ligands and 11 complexes were also studied.Graphical abstractFour thioether ligands containing pyridine and quinoline groups were designed and coordinated with transition metals into 11 complexes with various kinds of structural modes. The biological activities of the ligands and complexes were studied comparatively.Highlights► Four thioether ligands containing pyridine and quinoline groups were synthesized. ► Transition metal complexes with various kinds of coordination modes were assembled. ► The ligands and complexes show efficient biological activities.
Co-reporter:Qiong-Yan Yu ; Jin-Yun Liao ; Shi-Ming Zhou ; Yong Shen ; Jun-Min Liu ; Dai-Bin Kuang
The Journal of Physical Chemistry C 2011 Volume 115(Issue 44) pp:22002-22008
Publication Date(Web):September 27, 2011
DOI:10.1021/jp2054519
Three organic dyes incorporating a disubstituted triphenyl-amine unit as the electron donor, a thiophene moiety as the conjugated spacer, and 2-cyanoacrylic acid as the electron acceptor, have been synthesized and applied for the dye-sensitized solar cells (DSSCs). The conversion efficiencies of the DSSCs range from 4.99 to 6.04%. The influence of the hydrophobic hydrocarbon chain length of the substituent group in these dyes on the device performance in DSSCs has been investigated. It was found that the dyes with longer hydrocarbon chains gave higher photocurrents, open-circuit voltages, and efficiency values, which may derive from the higher molar absorption coefficient of metal-to-ligand charge transfer (MLCT), more appropriate localization of the frontier orbitals and longer electron lifetimes. We attribute the importance of the lengthening of the anchoring groups to the role of the dye as a better absorber for the incoming light and longer blocking layer to avoid charge recombination.
Co-reporter:JiJun Jiang;Rui Yang;Ying Xiong;Lei Li;Mei Pan;ChengYong Su
Science China Chemistry 2011 Volume 54( Issue 9) pp:
Publication Date(Web):2011 September
DOI:10.1007/s11426-011-4348-1
Reaction of Zn(NO3)2·6H2O with 5-(isonicotinamido) isophthalic acid (H2INAIP) in N,N-dimethylformamide (DMF) affords a new three-dimensional (3D) coordination polymer {[Zn(INAIP)(DMF)]·0.5DMF·4H2O}n (1). The X-ray crystallographic structural analysis reveals that complex 1 is a 3D porous framework containing a potential open metal site inside the pores. Topology analysis confirms that complex 1 is a two-fold interpenetrated (10, 3)-b net with both metal ion and ligand acting as 3-connecting nodes. The thermal stability, variable temperature X-ray diffraction pattern and N2 adsorption property of the complex are investigated.
Co-reporter:Ji-Jun Jiang ; Mei Pan ; Jun-Min Liu ; Wei Wang
Inorganic Chemistry 2010 Volume 49(Issue 21) pp:10166-10173
Publication Date(Web):September 29, 2010
DOI:10.1021/ic1014384
By using the tripodal ligand ntb (tris(benzimidazole-2-ylmethyl)amine) and lanthanide nitrate, three isomorphous series of coordination frameworks of the general formula [Ln(ntb)(NO3)3]·solvents (series 1: monoclinic C2/c, Ln = Gd3+ and Yb3+; series 2: hexagonal P31/c, Ln = Nd3+, Eu3+, Gd3+, and Er3+; series 3, cubic Pa3̅, Ln = Gd3+ and Er3+; solvent = H2O or CH3OH) have been assembled and characterized with IR, elemental analyses, and single crystal and powder X-ray diffraction methods. In all isomorphous complexes, analogous [Ln(ntb)(NO3)3] coordination monomers of the same structure act as the building blocks to be assembled via hydrogen bonds into three-dimensional (3D) frameworks. So the complexes of the same lanthanide ion (for example, the Gd3+ ion) from three isomorphous series form polymorphs, for example, monoclinic polymorph 1-Gd, hexagonal polymorph 2-Gd, and cubic polymorph 3-Gd. The single-crystal analyses revealed that the polymorphism was related to different fashions of hydrogen bonding interactions, which was caused by different crystallization conditions, leading to the formation of different 3D hydrogen-bonded frameworks showing distinct porous and topological structures. The monoclinic and hexagonal crystals contain 1D channels, while the cubic crystal is nonporous. The thermogravimetric analyses indicated that all polymorphic crystals have high thermal stability against the removal of guest molecules, and the robust porosity of the hexagonal crystals has been verified by temperature-dependent single-crystal-to-single-crystal measurements upon guest removal/uptake. The solvents adsorption study disclosed that the porous frameworks show high selectivity of benzene against toluene and xylene, while the gas adsorption measurements indicated a moderate H2, CO2, and MeOH storage capacity in contrast to low N2 uptake. The solid-state photoluminescence of the Eu3+ and Nd3+ complexes in the near-infrared and visible region has also been investigated, offering examples with optical properties tunable by means of isomorphous replacement.
Co-reporter:Qian Zhang, Jianyong Zhang, Qiong-Yan Yu, Mei Pan and Cheng-Yong Su
Crystal Growth & Design 2010 Volume 10(Issue 9) pp:4076-4084
Publication Date(Web):August 5, 2010
DOI:10.1021/cg100742c
Two semirigid ditopic ligands, 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L1) and 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene (L2), reacted with Ag+ salts to result in two series of complexes, namely [Ag2(L1)2](CF3SO3)2 (1-R), [Ag2(L1)3](CF3SO3)2 (1-C), {[Ag2(L1)3](CF3SO3)2·CH3CN}n (1-P), and [Ag2(L2)2](ClO4)2·1.5CH3CN (2-R), {[Ag3(L2)2](ClO4)3}n (2-P). All complexes have been structurally characterized by single-crystal X-ray diffraction with the phase purity of bulk samples attested by powder X-ray diffraction (PXRD). Four types of structures are formed: (1) a discrete M2L2 ring with two Ag+ ions and two cis-L ligands comprising a molecular rectangle (1-R and 2-R), (2) a discrete M2L3 cage with two Ag+ ions and three cis-L ligands comprising a trigonal cage (1-C), (3) a one-dimensional [M2L3]n loop-and-chain with 3-connecting Ag+ ions bridged by both cis- and trans-L ligands (1-P), and (4) a two-dimensional [M2L3]n network of (6,3) topology with 3-connecting Ag+ ions bridged by trans-L ligands (2-P). The M2L3 cage 2-C was not obtained as a solid-state complex but observable in solution by ESI mass spectrometry. The complexes 1-C, 1-P and 2-C, 2-P contain comparable 3-connecting M2L3 building blocks, constituting two pairs of ring-opening isomers corresponding to single ring-opening (1-C to 1-P) and double ring-opening (2-C to 2-P) polymerization processes via cis-L to trans-L ligand conformation change, respectively. Investigations on solution behaviors by 1H NMR and ESI-MS and structural conversions monitored by PXRD disclose that the thermodynamically favored M2L2 ring can be converted to a thermodynamically disfavored M2L3 cage in solution through an L addition mechanism, which causes crystallization of isomeric structures of an M2L3 cage or [M2L3]n polymer due to ring-opening isomerization. Formation of an M2L3 cage or [M2L3]n polymer is influenced by kinetic or thermodynamic effects as well as the solubility-product constant (Ksp), implying predictable syntheses by controlling the crystallization conditions.
Co-reporter:Qian Zhang, Lisi He, Jun-Min Liu, Wei Wang, Jianyong Zhang and Cheng-Yong Su
Dalton Transactions 2010 vol. 39(Issue 46) pp:11171-11179
Publication Date(Web):21 Oct 2010
DOI:10.1039/C0DT00406E
M2L2 type metallacyclic complexes, [Pd2(L1)2Cl4]·1.5CH2Cl2 (1), [Pd2(L1)2Cl4]·2CHCl3 (2), [Pd2(L2)2Cl4]·2CH2Cl2·2CH3CN (3), [Pd2(L2)2Cl4]·2CHCl3·2CH3CN (4) and [Pd2(L3)2Cl4]·CH2Cl2·2CH3CN (5), have been prepared from three semi-rigid benzimidazol or benzotriazol ligands, 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L1), 1,4-bis(5,6-dimethylbenzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L2) and 1,4-bis(benzotriazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L3). All the complexes were structurally characterized by single-crystal X-ray diffraction and the phase purity was confirmed by powder X-ray diffraction (PXRD) measurements. The solution structure of representative complex 1 was studied by 1H NMR titration and ESI mass spectroscopy. The thermal stability and guest-exchange properties of 1, 3 and 4 were investigated, revealing that the Pd2L2 metallacycles can act as a selective receptor for CH2Cl2 or CHCl3 guest molecules. The catalytic activity of 1 in Suzuki–Miyaura coupling reaction was also studied and 1 could be recycled at least 5 times under heterogeneous conditions, indicative of a potential self-supported catalyst.
Co-reporter:Ji-Jun Jiang;Lei Li;Mei-Hua Lan;Mei Pan;Andreas Eichhöfer Dr.;Dieter Fenske
Chemistry - A European Journal 2010 Volume 16( Issue 6) pp:1841-1848
Publication Date(Web):
DOI:10.1002/chem.200901929
Abstract
Two series of microporous lanthanide coordination networks of the general formula, {[Ln(ntb)Cl3]⋅x H2O}n (series 1: monoclinic C2/c, Ln=Sm and Tb; series 2: hexagonal P31/c, Ln=Sm and Eu; ntb=tris(benzimidazol-2-ylmethyl)amine, x=0–4) have been synthesized and characterized by IR, elemental analyses, thermal gravimetry, and single-crystal and powder X-ray diffraction methods. In both series, the monomeric [Ln(ntb)Cl3] coordination units are consolidated by NH⋅⋅⋅Cl or CH⋅⋅⋅Cl hydrogen bonds to sustain three-dimensional (3D) networks. However, the different modes of hydrogen bonding in the two series lead to crystallization of the same [Ln(ntb)Cl3] monomers in different forms (monoclinic vs. hexagonal), consequently giving rise to distinct porous structures. The resulting hydrogen-bonded coordination networks display high thermal stability and robustness in water removal/inclusion processes, which was confirmed by temperature-dependent single-crystal-to-single-crystal transformation measurements. Adsorption studies with H2, CO2, and MeOH have been carried out, and reveal distinct differences in adsorption behavior between the two forms. In the case of MeOH uptake, the monoclinic network shows a normal type I isotherm, whereas the hexagonal network displays dynamic porous properties.
Co-reporter:Rui Yang;Lei Li;Ying Xiong;Dr. Jian-Rong Li;Dr. Hong-Cai Zhou;Dr. Cheng-Yong Su
Chemistry – An Asian Journal 2010 Volume 5( Issue 11) pp:2358-2368
Publication Date(Web):
DOI:10.1002/asia.201000218
Abstract
Assembly of copper(I) halide with a new tripodal ligand, benzene-1,3,5-triyl triisonicotinate (BTTP4), afforded two porous metal–organic frameworks, [Cu2I2(BTTP4)]⊃2 CH3CN (1⋅2 CH3CN) and [CuBr(BTTP4)]⊃(CH3CN⋅CHCl3⋅H2O) (2⋅solvents), which have been characterized by IR spectroscopy, thermogravimetry (TG), single-crystal, and powder X-ray diffraction (PXRD) methods. Compound 1.CH3CN is a polycatenated 3D framework that consists of 2D (6,3) networks through inclined catenation, whereas 2 is a doubly interpenetrated 3D framework possessing the ThSi2-type (ths) (10,3)-b topology. Both frameworks contain 1D channels of effective sizes 9×12 and 10×10 Å2, which amounts to 43 and 40 % space volume accessible for solvent molecules, respectively. The TG and variable-temperature PXRD studies indicated that the frameworks can be completely evacuated while retaining the permanent porosity, which was further verified by measurement of the desolvated complex [Cu2I2(BTTP4)] (1′). The subsequent guest-exchange study on the solvent-free framework revealed that various solvent molecules can be adsorbed through a single-crystal-to-single-crystal manner, thus giving rise to the guest-captured structures [Cu2I2(BTTP4)]⊃C6H6 (1.benzene), [Cu2I2(BTTP4)]⊃2 C7H8 (1.2toluene), and [Cu2I2(BTTP4)]⊃2 C8H10 (1.2ethyl benzene). The gas-adsorption investigation disclosed that two kinds of frameworks exhibited comparable CO2 storage capacity (86–111 mL g−1 at 1 atm) but nearly none for N2 and H2, thereby implying its separation ability of CO2 over N2 and H2. The vapor-adsorption study revealed the preferential inclusion of aromatic guests over nonaromatic solvents by the empty framework, which is indicative of selectivity toward benzene over cyclohexane.
Co-reporter:Yong-Ru Liu, Lisi He, Jianyong Zhang, Xiaobing Wang and Cheng-Yong Su
Chemistry of Materials 2009 Volume 21(Issue 3) pp:557
Publication Date(Web):January 9, 2009
DOI:10.1021/cm802841r
A series of metal−organic gels (MOGs) were formed in CH3OH−CHCl3 solution based on L1 and Pd(COD)(NO3)2 (L1 = 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)tris(N-(pyridin-3-ylmethyl)benzamide, COD = cycloocta-1,5-diene) at different ratios. FT-IR, NMR, and fluorescence spectroscopy show that hydrogen bonding, π−π interaction, and coordination bonding are involved in the gel formation. The morphologies of these metallogels are Pd/L1 ratio dependent ranging from spheres to fibers. The fibrous networked gel shows higher catalytic activity in Suzuki−Miyaura coupling reaction than the spherical gel, acting as recyclable Pd(II) catalyst supported by the air-stable networked gel/xerogel.
Co-reporter:Ji-Jun Jang, Lei Li, Tao Yang, Dai-Bin Kuang, Wei Wang and Cheng-Yong Su
Chemical Communications 2009 (Issue 17) pp:2387-2389
Publication Date(Web):10 Mar 2009
DOI:10.1039/B820831J
Assembly of a tripodal ligand tris(2-benzimidazoylmethyl)amine with the long rod-like spacer N1,N4-bis(pyridin-4-ylmethylene)-benzene-1,4-diamine in the presence of M(ClO4)2 (M = Cd2+ and Mn2+) or H3O·ClO4 leads to formation of 63-hcb layers which interweave in a parallel fashion to give the first examples of hydrogen-bonding Borromean links.
Co-reporter:Guo-Bi Li, Jun-Min Liu, Zhi-Quan Yu, Wei Wang and Cheng-Yong Su
Inorganic Chemistry 2009 Volume 48(Issue 18) pp:8659-8661
Publication Date(Web):August 18, 2009
DOI:10.1021/ic9011263
A rare in situ metal/ligand reaction has been observed during the assembly of a maganese-coordination polymer under solvothermal conditions, which leads to double C−C coupling on CHCl3 involving cleavage of three C−Cl bonds and the formation of two new C−C bonds at the same carbon center.
Co-reporter:Qing Wang, Jianyong Zhang, Chun-Feng Zhuang, Yu Tang and Cheng-Yong Su
Inorganic Chemistry 2009 Volume 48(Issue 1) pp:287-295
Publication Date(Web):November 26, 2008
DOI:10.1021/ic801770n
Cd(II)/Mn(II) coordination grid networks containing large meshes have been assembled from a long rigid ligand, 2,5-bis(4′-(imidazol-1-yl)benzyl)-3,4-diaza-2,4-hexadiene (ImBNN), and M(CF3SO3)2 (M = Cd and Mn) salts, and their interpenetration change upon guest inclusion has been investigated with a series of aromatic molecules. Without guest molecules, the grid networks are triply interpenetrated to form closely packed layer structures [M(ImBNN)2(CF3SO3)2]n (M = Cd (1) and Mn (2)), but when guest molecules are introduced, the triply interpenetrated frameworks are changed to doubly interpenetrated ones with the inclusion of various aromatic molecules, namely, {[M(ImBNN)2(CF3SO3)2]⊃guest}n (M = Cd, guest = o-xylene (3), naphthalene (4), phenanthrene (5), and pyrene (6); M = Mn, guest = benzene (7), p-xylene (8), naphthalene (9), phenanthrene (10), and pyrene (11)). These complexes have been characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, and IR spectra. The guest-inclusion/desorption behaviors of representative complexes have been studied by thermogravimetric analyses and 1H NMR measurements. The grid networks display strong preference for aromatic guest inclusion, but less selectivity toward shape and size difference. Tuning of network interpenetration from 3-fold to 2-fold has been successfully achieved through the introduction of guest molecules, when the network displays flexibility to change cavity size to match the guest molecules.
Co-reporter:Sheng-Run Zheng, Qing-Yuan Yang, Rui Yang, Mei Pan, Rong Cao and Cheng-Yong Su
Crystal Growth & Design 2009 Volume 9(Issue 5) pp:2341
Publication Date(Web):March 10, 2009
DOI:10.1021/cg801228x
A new multifunctional semirigid Schiff-base ligand comprising two pyridyl (Py) and two benzimidazolyl (Bim) donor groups, 1,2-bis(1-(1-(pyridine-3-ylmethyl)benzimidazol-2-yl)ethylidene)hydrazine (L), has been synthesized, with which 10 coordination polymers of different transition metal ions, namely, {[AgL]CF3SO3·CH3OH}n (1), {[Ag2L](p-CH3C6H4SO3)2·2CH3OH}n (2), {[Hg3LCl6]·CHCl3}n (3), [HgLBr2]n (4), {[CdL(CH3CO2)2H2O]·1.5H2O}n (5), [CdLI2]n (6), {[MnL(H2O)4](ClO4)2·H2O}n (7), [MnL(p-CH3C6H4SO3)2]n (8), {[ZnL2(CH3CN)2(H2O)2](CF3SO3)2}n (9), and {[ZnL2(CH3CH2OH)2(H2O)2](p-CH3C6H4SO3)2}n (10) have been prepared and characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. In complexes 1, 2, and 3, L acts as a tetradentate ligand to connect four metal ions that show the same coordination environment in 1 or different coordination environments in 2 and 3, generating two-dimensional (2D) networks of the (4, 4) net topology. In complexes 4−8, L acts as a bidentate ligand to bridge two metal ions that display diversified coordination environments depending on coordination of the anions and/or water molecules. Complexes 4−7 have similar one-dimensional (1D) chain structures, while 8 is a three-dimensional (3D) framework with dia topology. In complexes 9 and 10, L acts as a monodentate ligand to form mononuclear coordination motifs. Besides versatile coordination modes, ligand L takes on different conformations responsive to donor affinity of different metal ions. In the case that the ligand L is bidentate or monodentate, there are Py and/or Bim groups free of coordination, thus being able to form hydrogen bonds through their noncoordinating NPy or NBim atoms. Therefore, the assembly processes are directed by synergistic effects involving metal−ligand coordination, hydrogen-bonding, π···π stacking, and other influencing factors such as solvents and counteranions.
Co-reporter:Hai-Ying Deng, Jian-Rong He, Mei Pan, Lei Li and Cheng-Yong Su
CrystEngComm 2009 vol. 11(Issue 5) pp:909-917
Publication Date(Web):07 Feb 2009
DOI:10.1039/B819608G
A new semirigid ditopic ligand, N,N′-bis(3-pyridylmethyl)naphthalene diimide (3-pmntd) has been synthesized, and five transition metal complexes, namely, [Cd2(3-pmntd)2I4]·2CHCl3 (1), [Hg(3-pmntd)Cl2]n (2), [Zn(3-pmntd)2(SCN)2]n (3), [Cd (3-pmntd)2(NO3)2]n (4) and {[Co2(3-pmntd)3(NO3)4]·2EtOH}n (5), have been obtained. Complex 1 forms discrete M2L2 metallacycles which are linked by C–H⋯O hydrogen bonds and π⋯π stacking interactions to result in a 2D layer. Complex 2 crystallizes in 1D chains which are further connected by C–H⋯O, C–H⋯Cl hydrogen bonds and π⋯π interactions into a 3D framework. Complexes 3 and 4 show a similar structural feature in the formation of non-interpenetrated 2D networks of (4,4) topology, while complex 5 displays a 2D network of (6,3) topology. The structural differences among these complexes are attributed to the different conformations adopted by the ligands, which are primarily induced by different metal centers with coordination environments restrained by different anions. Photoluminescent properties were also studied for selected complexes.
Co-reporter:Qing-Yuan Yang, Sheng-Run Zheng, Rui Yang, Mei Pan, Rong Cao and Cheng-Yong Su
CrystEngComm 2009 vol. 11(Issue 4) pp:680-685
Publication Date(Web):07 Jan 2009
DOI:10.1039/B813767F
Reaction of AgClO4 with a bulky semi-flexible tripodal ligand 2,4,6-tris(4-((pyridin-4-ylthio)methyl)phenyl)-1,3,5-triazine (tppt) affords highly undulating (6,3) honeycomb networks [Ag3(tppt)2](ClO4)3·8DMSO which display unusual net entanglement. Three (6,3) nets interweave in parallel to give rise to a 3-fold interpenetrating basic layer (2D → 2D parallel). In addition, every such layer interlocks four other layers, two above and two below (2D → 3D parallel). Therefore, totally fifteen (6,3) nets are involved in entanglement with respect to each basic layer, in which each single (6,3) net shows 11-fold interpenetration and 5-fold catenation, thus resulting in a novel 3D coordination polymer containing both interpenetration and polycatenation.
Co-reporter:Mei Pan, Xiang-Li Zheng, Yu Liu, Wei-Sheng Liu and Cheng-Yong Su
Dalton Transactions 2009 (Issue 12) pp:2157-2169
Publication Date(Web):03 Feb 2009
DOI:10.1039/B818322H
Six N-substituted NTB ligands (NTB = (tris(benzimidazol-2-ylmethyl)amine), namely, triMeNTB (L1), triEtNTB (L2), triPrNTB (L3), triBuNTB (L4), triAlNTB (L5) and triBzNTB (L6), have been synthesized through replacing the H atoms on the NH groups by methyl, ethyl, npropyl, nbutyl, allyl, and benzyl groups, respectively. Their corresponding Sm3+, Eu3+ and Tb3+ complexes consisting of different anions or secondary ligands have been prepared and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction measurements. Three types of structural models have been obtained: ML2 where two triTNTB ligands wrap around the Ln3+ ion with anions (ClO4− and CF3SO3−) free of coordination, MLA3 where one triRNTB ligand holds the Ln3+ ion with anions (Cl−, NO3− and picrate) participating in coordination, and MLL′3 where one triNTB ligand and three secondary antipyrine ligands coordinate with the Ln3+ ion. The Ln3+ ions in ML2 type complexes are 8-coordinating and display a slightly distorted cubic (LnN8) coordination geometry. The Ln3+ ions in MLA3 and MLL′3 types complexes show two different coordination geometries: one is 7-coordinating (MLA3 with Cl− anion and MLL′3), which can be described as a severely distorted cube short of one corner (LnN4Cl3 or LnN4O3), and the other is 10-coordinating (MLA3 with NO3− and picrate anions) which can be regarded as a severely distorted cube with one corner substituted by a three-atom cap (LnN4O6). The photoluminescent study reveals that the complexes with different Ln3+ ions show a general luminescent intensity tendency of Tb > Eu > Sm. The modification of the NTB molecule by altering R groups tunes the triplet states of the ligands and results in differentiable photophysical properties of the complexes. The anions or secondary ligand also have remarkable effects on the luminescent properties of the complexes.
Co-reporter:Chun-Feng Zhuang;Jianyong Zhang;Qing Wang;Zhao-Hua Chu;Dieter Fenske
Chemistry - A European Journal 2009 Volume 15( Issue 31) pp:7578-7585
Publication Date(Web):
DOI:10.1002/chem.200900552
Abstract
A doubly interpenetrated square-grid coordination polymer {[Cd(ImBNN)2(CF3SO3)2]⊃guest}n (1) (guest=C7H8 and ImBNN=2,5-bis[4′-(imidazol-1-yl)phenyl]-3,4-diaza-2,4-hexadiene) that contains cavities able to accommodate toluene guest molecules has been assembled by the reaction of the Schiff base ligand ImBNN and Cd(CF3SO3)2. The framework 1 shows dynamism in either temperature-dependent expansion and shrinkage or cooperatively temperature-dependent guest-driven ligand exchange at the metal center. Studies of guest removal/uptake by heating in a vacuum, cooling in air, and then heating in toluene at reflux have revealed a series of single-crystal-to-single-crystal structural transformations: complex 1 lost toluene guests and captured water molecules to give guest-free 1 b via a proposed metastable phase 1 a, and 1 b could readsorb toluene guests to give 1′, which represents a restored 1. These structural changes establish an indirect recoverable process that involves ligand exchange in the coordination sphere and guest exchange in the cavity accompanied by the cleavage/formation of CdO bonds and CF3SO3− anion-shifting. In contrast, direct heating of 1 in the absence of a vacuum resulted in thermostable 1 c, confirmed by X-ray powder diffraction as a new phase that could not be converted back into 1 and that had lost the ability of readsorbing toluene guests.
Co-reporter:Qi-Ting He;Xiang-Ping Li;Yu Liu;Zhi-Quan Yu;Wei Wang
Angewandte Chemie International Edition 2009 Volume 48( Issue 33) pp:6156-6159
Publication Date(Web):
DOI:10.1002/anie.200902276
Co-reporter:Qi-Ting He;Xiang-Ping Li;Yu Liu;Zhi-Quan Yu;Wei Wang
Angewandte Chemie 2009 Volume 121( Issue 33) pp:6272-6275
Publication Date(Web):
DOI:10.1002/ange.200902276
Co-reporter:Sheng-Run Zheng, Qing-Yuan Yang, Yong-Ru Liu, Jian-Yong Zhang, Ye-Xiang Tong, Cun-Yuan Zhao and Cheng-Yong Su
Chemical Communications 2008 (Issue 3) pp:356-358
Publication Date(Web):02 Nov 2007
DOI:10.1039/B711457E
Reaction of a rigid triangular ligand 2,4,6-tris[4-(1H-imidazole-1-yl)phenyl]-1,3,5-triazine (TIPT) with Cd2+ ions afforded rare non-interpenetrating CdI2-type networks which display high thermostability and potential porosity; the topological character of the CdI2-type networks have been analyzed in comparison with three common uniform (4,4), (6,3) and (3,6) plane nets.
Co-reporter:Ji-Jun Jiang ; Sheng-Run Zheng ; Yu Liu ; Mei Pan ; Wei Wang
Inorganic Chemistry 2008 Volume 47(Issue 22) pp:10692-10699
Publication Date(Web):October 15, 2008
DOI:10.1021/ic801516b
The synergistic interplay of coordination and hydrogen-bonding interactions leads to assembly of isomorphous compounds of the general formula [Ln(ntb)2](ClO4)3·(BDA4BPy)3·2MeCN}∞ (Ln = La, Sm and Pr, ntb = tris(2-benzimidazoylmethyl)amine, and BDA4BPy = N1,N4-bis(pyridin-4-ylmethylene)-benzene-1,4-diamine), of which polymorphic crystals can be isolated in a different solvent system. In acetonitrile (MeCN) solution, the compounds crystallize as a red color (Ln = La, meso-1, Ln = Pr, meso-2), while in an acetonitrile−benzonitrile (MeCN−PhCN) mixture, yellow crystals are obtained (Ln = Pr, helical-2). The single-crystal X-ray diffraction analyses of these crystals reveal that the structures display similar cylindrical arrays containing polycompartmental cavities for guest inclusion. Occurrence of polymorphism is due to formation of helical and meso-helical arrays, giving rise to a way to tune the helicity through the solvent effects on the helix propensity of the bis-tripodal coordination converters.
Co-reporter:Gao-Ren Li, Xi-Hong Lu, Wen-Xia Zhao, Cheng-Yong Su and Ye-Xiang Tong
Crystal Growth & Design 2008 Volume 8(Issue 4) pp:1276
Publication Date(Web):March 5, 2008
DOI:10.1021/cg7009995
The controllable electrochemical synthesis of Ce4+-doped ZnO nanostructures from nanotubes to nanorods and nanocages is reported. The electrochemical route for the preparation of Ce4+-doped ZnO nanostructures represents a simple, quick, and economical method. The growth mechanisms for Ce4+-doped ZnO nanotubes, nanorods, and nanocages are proposed here. Ce4+-doped ZnO nanotubes and nanocages formed when the crystal growth was only proceeded on the sides of six (101̅0) facets of a hexagonal planar nucleus with preferential growth in the (0001) direction. The hexagonal Ce4+-doped ZnO nanorods were formed when the crystal growth proceeded on the whole hexagonal planar nucleus with preferential growth in the (0001) direction. The X-ray diffraction, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and selected area electron diffraction were used to characterize the phase, composition, and qualities of the prepared Ce4+-doped ZnO nanotubes, nanorods, and nanocages. In addition, the photoluminescence properties of the prepared Ce4+-doped ZnO nanotubes, nanorods, and nanocages were investigated.
Co-reporter:Chun-Long Chen, Zhi-Quan Yu, Qian Zhang, Mei Pan, Jian-Yong Zhang, Cun-Yuan Zhao and Cheng-Yong Su
Crystal Growth & Design 2008 Volume 8(Issue 3) pp:897
Publication Date(Web):January 31, 2008
DOI:10.1021/cg070634i
Reaction of a flexible bis-bidentate ligand 1,4-bis(8-thioquinolyl)butane (C4TQ) with silver(I) salts afforded five complexes, namely, [Ag2(C4TQ)2](CF3SO3)2 (1), {[Ag(C4TQ)](CF3SO3)}n·0.5nCH3CN (2), [Ag2(C4TQ)2](ClO4)2 (3), {[Ag(C4TQ)](ClO4)}n (4), and {[Ag(C4TQ)(CH3CN)](ClO4)}n (5), of which 1 and 3 show dimeric M2L2 metallacycles while 2 and 4 show polymeric MnLn chains. The acetonitrile (MeCN) molecule in complex 2 is located in the crystal lattice without coordination to the Ag(I) ion. Therefore, two pairs of isomerized structures that retain the same compositions, [Ag2(C4TQ)2](CF3SO3)2 vs {[Ag(C4TQ)](CF3SO3)}n in complexes 1 and 2, as well as [Ag2(C4TQ)2](ClO4)2 vs {[Ag(C4TQ)](ClO4)}n in complexes 3 and 4, respectively, can be identified and regarded as ring-opening isomers. 1H NMR and electrospray ionization mass spectrometry studies in solution suggested that the cyclic and infinite structures were assembled from the same monomeric ML building blocks, which crystallized in different forms by dimerization or polymerization during the crystallization. The complex 5 also formed an infinite chain, but the MeCN molecule participated in coordination, indicating that the solvent and/or anion molecules may play a significant role in the assembly process. X-ray diffraction measurements and density functional theory calculations have been performed to track the structural conversion and elucidate the assembly mechanism.
Co-reporter:Qing Wang;Rui Yang;Chun-Feng Zhuang;Jian-Yong Zhang;Bei-Sheng Kang
European Journal of Inorganic Chemistry 2008 Volume 2008( Issue 10) pp:1702-1711
Publication Date(Web):
DOI:10.1002/ejic.200701106
Abstract
Four double-strand one-dimensional (1D) coordinationpolymers, namely, {[Ni(N3Py)2(NO3)2]·(C6H6)x·C2H5OH}n (1), [Cd(ImBNN)2(CH3C6H4SO3)2]n (2), {[Co(N3OPy)2(H2O)2](ClO4)2·C6H6·H2O}n (3), and {[Co(N3OPy)2(H2O)2](ClO4)2·(C8H10)x}n (4) were obtained from the assembly of three N,N′-type Schiff base ligands, 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (N3Py), 2,5-bis(4′-(imidazol-1-yl)benzyl)-3,4-diaza-2,4-hexadiene (ImBNN), and bis[4-(3-pyridylmethylenemino)phenoxy]methane (N3OPy), with transition-metal ions. All complexes were characterized by single-crystal X-ray diffraction, X-ray powder diffraction, and FTIR measurements. The guest-inclusion behavior of these complexes were investigated by thermogravimetric and X-ray powder diffraction analyses. The structural relationship between the ligands and the cavity sizes and packing fashions have been discussed to elucidate the distinctive guest-inclusion behavior of these complexes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Co-reporter:Chun-Long Chen, Qian Zhang, Jun-Hua Yao, Jian-Yong Zhang, Bei-Sheng Kang, Cheng-Yong Su
Inorganica Chimica Acta 2008 Volume 361(9–10) pp:2934-2940
Publication Date(Web):27 June 2008
DOI:10.1016/j.ica.2008.02.062
The one-dimensional (1D) meso polymeric structure {[Cd2(HL)(N3)2(H2O)] · (DMF)3}n2 has been assembled from a propeller-like chiral mononuclear complex {[Cd(H3L)(H2O)][Cd(H3L)(H2O)2]}(ClO4)41 (H3L = tris(5-methyl-2-benzimidazolylmethyl)amine). The assembly process was achieved by the aid of NaN3 which causes N-deprotonation of the 5-methyl-benzimidazole groups and bridges the opposite enantiomers to form 1D meso chain. Both the monomer 1 and polymer 2 have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and infrared spectroscopy. The ESI-MS of complex 1 has been studied to understand the assembly process. The photoluminescence measurements of the ligand and the complexes show that the ligand-based emission has been significantly enhanced in the monomer while little changed after polymerization.One-dimensional meso coordination polymer has been assembled from enantiomeric monomers which significantly intensifies the ligand-based luminescence.
Co-reporter:Xue-Li Zhang, Cui-Ping Guo, Qing-Yuan Yang, Wei Wang, Wei-Sheng Liu, Bei-Sheng Kang and Cheng-Yong Su
Chemical Communications 2007 (Issue 41) pp:4242-4244
Publication Date(Web):07 Aug 2007
DOI:10.1039/B709118D
Reaction of two tripodal ligands, 2,4,6-tris(4-((2-methyl-benzimidazol-1-yl)methyl)phenyl)-1,3,5-triazine (L111) and 1,3,5-tris(4-((2-methyl-benzimidazol-1-yl)methyl)phenyl)benzene (L222), with AgSbF6 led to formation of two types (6,3) networks in one single crystal, of which one is three-fold Borromean topologically entangled while the other is independent, showing the same chirality and sandwiched Borromean stacking.
Co-reporter:Xiang-Ping Li, Mei Pan, Sheng-Run Zheng, Yong-Ru Liu, Qi-Ting He, Bei-Sheng Kang and Cheng-Yong Su
Crystal Growth & Design 2007 Volume 7(Issue 12) pp:2481
Publication Date(Web):November 15, 2007
DOI:10.1021/cg070080j
Two asymmetric ligands, 2-(3-pyridyl)benzimidazole (3-PyBim) and 2-(4-pyridyl)benzimidazole (4-PyBim) which are positional isomers and versatile to provide both coordination donors (NPy and NBim) and hydrogen bonding sites (NBim and HNBim), were utilized to synthesize a series of transition metal complexes, namely [Ag2(3-PyBim)2](X)2 (X = BF4– (1), NO3– (2), ClO4– (3), CF3SO3– (4)), [Ag(4-PyBim)](NO3)·(H2O) (5), [Cu(3-PyBim)2(H2O)2](ClO4)2 (6), [Co(3-PyBim)2(H2O)4](NO3)2·(H2O)4(7), [Cu(4-PyBim)2(Cl)2](H2O)2 (8), [Zn(4-PyBim)2(H2O)2(NO3)2] (9), and [Cu2(3-PyBim)2(OAc)4] (10). These simple complexes show diversified intermolecular interaction modes and can behave as basic structural units to be assembled into higher dimensional structures via dimension increasing. In complexes 1–4, every two Ag (I) atoms are connected by two 3-PyBim ligands to form a discrete [Ag2(PyBim)2]2+ cyclic unit, while in complex 5, Ag (I) atoms are bridged by 4-PyBim ligands into a one-dimensional “zigzag” chain. This is due to positional isomerization of the ligands 3-PyBim and 4-PyBim, but they both display the similar end-to-end coordination mode. In contrast, these two ligands show the end-on coordination mode in complexes 6–9 with the Cu (II), Co (II), or Zn (II) ions taking on square or octahedral coordination geometries to form monomeric structural units containing one metal and two ligands, as well as additional water molecules or counteranions wherever necessary. In complex 10, the well-known dimetal paddle-wheel motif is formed with two Cu (II) ions adopting a square pyramidal geometry, but the two 3-PyBim ligands also take the same end-on coordination mode as that in complexes 6–9. The different coordination modes of the ligands in together with the influences from the counteranions play essential roles to propagate these basic structural units into 1D (1, 10), 2D (2–6, 8), or 3D (7, 9) frameworks via hydrogen bonding and other weak interactions. Thermogravimetric properties of some complexes were also measured.
Co-reporter:Chun-Long Chen;Jian-Yong Zhang
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 19) pp:
Publication Date(Web):23 MAY 2007
DOI:10.1002/ejic.200700187
This microreview covers recent advances in the assembly of coordination molecular architectures showing cyclic, prismatic and tubular structures based on the semi-rigid or flexible ligands. Four assembly routes are outlined depending on the symmetry interactions between specific ligands and metal ions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Xiang-Ping Li, Jian-Yong Zhang, Yu Liu, Mei Pan, Sheng-Run Zheng, Bei-Sheng Kang, Cheng-Yong Su
Inorganica Chimica Acta 2007 Volume 360(Issue 9) pp:2990-2996
Publication Date(Web):10 June 2007
DOI:10.1016/j.ica.2007.02.024
The crystal structures of four Ag(I) and Hg(II) complexes of the ligand 1,4-bis(1-benzyl-benzimidazol-2-yl)cyclohexane (N-BBzBimCH) have been described, that is, [Hg2(N-BBzBimCH)Cl4] (1), [Hg(N-BBzBimCH)Br2] (2), [Ag(N-BBzBimCH)](NO3)(H2O) (3) and [Ag2(N-BBzBimCH)(CF3OCO)2] (4). All these compounds show 1D polymeric structures in the solid state. In complexes 1 and 4, the chloride ions and the trifluoroacetate groups bridge the [Hg2(N-BBzBimCH)Cl2] and [Ag2(N-BBzBimCH)] fragments, respectively, to generate 1D polymers. While the bromide ions in complex 2 and nitrate groups in complex 3 are only serving as terminal ligands to suffice the coordination geometry of the metal centers. In all cases, weak intermolecular interactions such as C–H⋯X (X = Cl, Br) contacts, hydrogen bonds, π–π interactions and C–H⋯π stacking play important roles to extend the 1D chain structures to 2D network. Solid state fluorescence of these compounds was also studied.Four one-dimensional Ag(I) and Hg(II) complexes of a newly synthesized ligand 1,4-bis(1-benzyl-benzimidazol-2-yl)cyclohexane (N-BBzBimCH) have been reported, in which different counter anions play different roles to sustain the chain structure. Various weak intermolecular interactions such as C–H⋯X (X = Cl, Br) contacts, hydrogen bonds, π–π interactions and C–H⋯π stacking also play important roles to extend the 1D chain structures into 2D network.
Co-reporter:Xiang-Li Zheng;Yu Liu;Mei Pan Dr.;Xing-Qiang Lü Dr.;Jian-Yong Zhang Dr.;Cun-Yuan Zhao Dr.;Ye-Xiang Tong Dr. Dr.
Angewandte Chemie 2007 Volume 119(Issue 39) pp:
Publication Date(Web):15 AUG 2007
DOI:10.1002/ange.200702401
Himmelblaue Forschung: Untersuchungen zur Photo- und Elektrolumineszenz einer Serie von Ce3+-Komplexen mit Benzimidazol-Tripodliganden ergaben einen effektiven Energietransfer von metall- wie ligandenbasierten Übergängen und eine effiziente blaue metallzentrierte Emission. Eine blau emittierende Leuchtdiode, die mit einem solchen Cerkomplex hergestellt wurde, erwies sich als funktionsfähig.
Co-reporter:Xiang-Li Zheng;Yu Liu;Mei Pan Dr.;Xing-Qiang Lü Dr.;Jian-Yong Zhang Dr.;Cun-Yuan Zhao Dr.;Ye-Xiang Tong Dr. Dr.
Angewandte Chemie International Edition 2007 Volume 46(Issue 39) pp:
Publication Date(Web):15 AUG 2007
DOI:10.1002/anie.200702401
Sky-blue research: Studies of the photoluminescence and electroluminescence of a series of Ce3+ coordination complexes with tripodal benzimidazole ligands reveals effective energy transfer from both metal- and ligand-based transitions and efficient blue metal-centered emission. A blue-emitting LED device was fabricated using one such cerium complex, suggesting their potential application as light-emitting materials.
Co-reporter:Ji-Jun Jiang, Xiang-Ping Li, Xue-Li Zhang, Bei-Sheng Kang and Cheng-Yong Su
CrystEngComm 2005 vol. 7(Issue 99) pp:603-607
Publication Date(Web):18 Oct 2005
DOI:10.1039/B512098E
A non-interpenetrating two-dimensional Ag(I)–4,4′-bipyridine coordination polymer of (6,3) topology has been assembled from the reaction of 4,4-bipyridine with AgSbF6. Large twelve-membered Ag6(4,4′-bipy)6 hexagonal rings with dimensions 17 × 26 Å
(atom-to-atom separation) are formed which share edges to fabricate the honeycomb network. Parallel stacking of these honeycomb networks in an offset way affords 1D tubular ‘channels’ hosting SbF6− anions.
Co-reporter:Yu-Jie Dong, Hua-Shang Rao, Yang Cao, Hong-Yan Chen, Dai-Bin Kuang, Cheng-Yong Su
Journal of Power Sources (1 March 2017) Volume 343() pp:148-155
Publication Date(Web):1 March 2017
DOI:10.1016/j.jpowsour.2017.01.051
Co-reporter:Li-Lin Tan, Jian-Feng Huang, Yong Shen, Li-Min Xiao, Jun-Min Liu, Dai-Bin Kuang and Cheng-Yong Su
Journal of Materials Chemistry A 2014 - vol. 2(Issue 24) pp:NaN8994-8994
Publication Date(Web):2014/04/17
DOI:10.1039/C4TA01351D
Two new D–D–π–π–A type stable organic sensitizers, DT3 and DW3, were successfully synthesized for dye-sensitized solar cells (DSSCs). DT3 displayed η values of 10.03% and 8.05% in liquid and quasi-solid-state DSSCs, respectively, under standard global 1.5 solar conditions, offering an example achieving the highest efficiency to date in quasi-solid-state DSSCs based on pure organic dyes.
Co-reporter:Qing-Yuan Yang, Kang Li, Jian Luo, Mei Pan and Cheng-Yong Su
Chemical Communications 2011 - vol. 47(Issue 14) pp:NaN4236-4236
Publication Date(Web):2011/02/25
DOI:10.1039/C0CC05464J
Reaction of a semi-rigid tripodal ligand 1,1′,1′′-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)tripyridinium-4-olate) (TTP) with Ln3+ (Ln = Eu, Gd) afforded rare (3,12)-connected metal–organic frameworks (MOFs). A topological simplification of such highly connected 3D MOFs on the basis of 2D CdI2 (3,6)-nets is proposed. The luminescent and anion exchange properties of the compounds were determined.
Co-reporter:Lianfen Chen, Jian Kang, Hao Cui, Yingxia Wang, Lan Liu, Li Zhang and Cheng-Yong Su
Dalton Transactions 2015 - vol. 44(Issue 27) pp:NaN12188-12188
Publication Date(Web):2015/02/19
DOI:10.1039/C4DT03782K
A series of homochiral metal–organic cages (MOCs) have been obtained from self-assembly of Cu(II) salts with chiral N,N′-(bicyclo[2,2,2]oct-7-ene-tetracarboxylic)-bis-amino acids. Single-crystal X-ray diffraction analyses reveal that these compounds show a lantern-type cage structure, in which one pair of Cu2(CO2)4 paddlewheels is linked by four diacid ligands. The resulting homochiral cages have been fully characterized by EA, TOF-MS, TGA, VTPXRD, IR, UV, and CD measurements. The catalytic tests reveal that these Cu(II) cages are effective in cyclopropanation with excellent diastereoselectivity (up to 99:1 E/Z). In addition, the cage catalysts can promote the aziridination reaction with PhINNs.
Co-reporter:Sujuan Wang, Lei Li, Jianyong Zhang, Xiaochen Yuan and Cheng-Yong Su
Journal of Materials Chemistry A 2011 - vol. 21(Issue 20) pp:NaN7104-7104
Publication Date(Web):2011/03/31
DOI:10.1039/C1JM10394F
A structurally flexible porous metal–organic framework, [CuII(bped)2(H2O)2(SiF6)] ⊃ 4H2O (Cu-MOF-SiF6) was prepared from CuSiF6 and meso-1,2-bis(4-pyridyl)-1,2-ethanediol (bped) in EtOH–H2O. Cu-MOF-SiF6 is a three-dimensional (3D) polycatenated framework consisting of two-dimensional (2D) (4,4) topological grid networks which display 2-fold inclined interpenetration in the crystal lattice. The SiF62− anions hosted in the one-dimensional channels of Cu-MOF-SiF6 can be readily exchanged with NO3− anions while keeping the framework intact, leading to isomorphous Cu-MOF-NO3. The Cu-MOFs show selective adsorption behaviors due to the host–guest interaction, which is dependent on the anions and the guest size. The MeOH uptake investigation indicates that Cu-MOF-SiF6 demonstrates a breathing effect, while Cu-MOF-NO3 exhibits distinctive stepwise MeOH sorption due to the smaller size of NO3− and the larger voids in the crystal lattice. Cu-MOF-NO3 also exhibits stepwise sorption for larger EtOH guests, while the uptake of EtOH is blocked in Cu-MOF-SiF6. In addition, the solids show anion-responsive catalytic properties. Both Cu-MOF-SiF6 and Cu-MOF-NO3 efficiently oxidize benzylic compounds to the corresponding carbonyl functionality under mild and convenient reaction conditions, but improved catalytic activity was observed for Cu-MOF-NO3. The catalysts can be reused with the framework left intact at least three times without losing of any activity.
Co-reporter:Ying Xiong, Yan-Zhong Fan, Rui Yang, Sha Chen, Mei Pan, Ji-Jun Jiang and Cheng-Yong Su
Chemical Communications 2014 - vol. 50(Issue 93) pp:NaN14634-14634
Publication Date(Web):2014/09/22
DOI:10.1039/C4CC06697A
By stepwise functionalization of a T-shaped ligand with amide and N-oxide groups, we obtained a MOF with drastically strengthened CO2–framework interactions, induced by a “open donor sites” (ODSs) effect, resulting in a high heat of adsorption and high CO2/CH4, CO2/CO and CO2/N2 separation selectivities at room temperature.
Co-reporter:Yi-Fan Chen, Jun-Min Liu, Jian-Feng Huang, Li-Lin Tan, Yong Shen, Li-Min Xiao, Dai-Bin Kuang and Cheng-Yong Su
Journal of Materials Chemistry A 2015 - vol. 3(Issue 15) pp:NaN8090-8090
Publication Date(Web):2015/03/03
DOI:10.1039/C5TA00332F
Two novel arylamine-free organic compounds (CYF1 and CYF2) incorporating a substituted benzo[1,2-b:4,5-b′]dithiophene unit as the electron donor were synthesized and used as sensitizers for dye-sensitized solar cells (DSSCs). The relationship between the chemical structure and photovoltaic performance was investigated. A higher molar absorption coefficient, longer electron lifetime, and larger adsorption amount were observed for sensitizer CYF1, which contains a single π bridge and anchoring unit, compared with CYF2 with twin π bridges and anchoring units. As a result, under standard global AM 1.5 solar conditions, the device based on CYF1 sensitizer gave a higher conversion efficiency of 8.02% than that based on CYF2. This is the highest value for amine-free organic sensitizers with no strong donor units. Moreover, the CYF1- and CYF2-sensitized DSSCs exhibited excellent stability under 1000 W m2 light soaking at 60 °C for 600 h. This is the first example of organic sensitizers based on benzo[1,2-b:4,5-b′]dithiophene donors for efficient dye-sensitized solar cells.
Co-reporter:Xue-Li Zhang, Cui-Ping Guo, Qing-Yuan Yang, Wei Wang, Wei-Sheng Liu, Bei-Sheng Kang and Cheng-Yong Su
Chemical Communications 2007(Issue 41) pp:NaN4244-4244
Publication Date(Web):2007/08/07
DOI:10.1039/B709118D
Reaction of two tripodal ligands, 2,4,6-tris(4-((2-methyl-benzimidazol-1-yl)methyl)phenyl)-1,3,5-triazine (L111) and 1,3,5-tris(4-((2-methyl-benzimidazol-1-yl)methyl)phenyl)benzene (L222), with AgSbF6 led to formation of two types (6,3) networks in one single crystal, of which one is three-fold Borromean topologically entangled while the other is independent, showing the same chirality and sandwiched Borromean stacking.
Co-reporter:Sheng-Run Zheng, Qing-Yuan Yang, Yong-Ru Liu, Jian-Yong Zhang, Ye-Xiang Tong, Cun-Yuan Zhao and Cheng-Yong Su
Chemical Communications 2008(Issue 3) pp:NaN358-358
Publication Date(Web):2007/11/02
DOI:10.1039/B711457E
Reaction of a rigid triangular ligand 2,4,6-tris[4-(1H-imidazole-1-yl)phenyl]-1,3,5-triazine (TIPT) with Cd2+ ions afforded rare non-interpenetrating CdI2-type networks which display high thermostability and potential porosity; the topological character of the CdI2-type networks have been analyzed in comparison with three common uniform (4,4), (6,3) and (3,6) plane nets.
Co-reporter:Lu-Yin Zhang, Ya-Jun Hou, Mei Pan, Ling Chen, Yi-Xuan Zhu, Shao-Yun Yin, Guang Shao and Cheng-Yong Su
Dalton Transactions 2015 - vol. 44(Issue 34) pp:NaN15219-15219
Publication Date(Web):2015/04/13
DOI:10.1039/C5DT00545K
Four Ru(II)/Ir(III) metalloligands have been designed and synthesized from polypyridine and bibenzimidazole (BiBzIm) organic ligands, which show strong visible light absorption via metal-to-ligand charge transfer (MLCT) transitions. Nd/Yb(III) complexes were further assembled from these Ru(II)/Ir(III) metalloligands, and Ln(III)-centered NIR emissions can be efficiently sensitized by 3MLCT states of the metalloligands in the visible-light region. The energy transfer rates for the complexes are generally in the order Nd > Yb, which is due to the better matching between 3MLCT states of Ru(II)/Ir(III) metalloligands and densely distributed excited states of Nd(III) ions. Long decayed lifetimes on a μs scale and high quantum yields up to 1% are obtained in these lanthanide complexes, suggesting that the Ru(II)/Ir(III) metalloligands can serve as a good visible light harvesting antenna to efficiently sensitize Ln(III)-based NIR luminescence.
Co-reporter:Guo-Bi Li, Jian-Rong He, Mei Pan, Hai-Ying Deng, Jun-Min Liu and Cheng-Yong Su
Dalton Transactions 2012 - vol. 41(Issue 15) pp:NaN4633-4633
Publication Date(Web):2012/02/29
DOI:10.1039/C2DT11815G
Four semirigid ditopic ligands, N,N′-bis(3-pyridylmethyl)-pyromellitic diimide (L11), N,N′-bis(4-pyridylmethyl)-pyromellitic diimide (L22), N,N′-bis(3-pyridylmethyl)-naphthalene diimide (L33), and N,N′-bis(4-pyridylmethyl)-naphthalene diimide (L44), reacted with Cd(NO3)2 to result in four cadmium(II) complexes, namely, {[Cd2(L11)2(NO3)4(CH3OH)4]·H2O} (1), [Cd(L22)(NO3)2(CH3OH)2·Cd2(L22)3(NO3)4]·{4(HCCl3)·2H2O}n (2), {[Cd(L33)2(NO3)2]}n (3), and {[Cd(L44)2(NO3)2]·2(CHCl3)}n (4). These complexes have been characterized by elemental analyses, powder X-ray diffraction, thermogravimetric (TG) analyses, IR spectroscopy, and single-crystal X-ray diffraction. Structural analyses show that four types of structures are formed: (1) a discrete M2L2 ring with two Cd ions and two cis-L11 ligands comprising a zero-dimensional molecular rectangle (0D), (2) an unusual zigzag linear chain and a one-dimensional ladder existing simultaneously in the crystal lattice (1D), (3) a two-dimensional network of the (4,4) net structure (2D), and (4) an unusual chiral three-dimensional framework with 5-fold interpenetrating diamond (dia) topology (3D). In these complexes, the ligands exhibit different coordination modes and construct various architectures by bridging Cd(NO3)2 inorganic building blocks. These results suggest that structural diversity of the complexes is tunable by ligand modifications, that is, varying the ligand spacer bulkiness or substituent position of terminal group. Furthermore, gas adsorption measurements indicate that 4 possesses moderate CO2 uptake and some adsorption selectivity for CO2 over N2.
Co-reporter:Xiaobing Wang, Jing Huang, Shenglin Xiang, Yu Liu, Jianyong Zhang, Andreas Eichhöfer, Dieter Fenske, Shi Bai and Cheng-Yong Su
Chemical Communications 2011 - vol. 47(Issue 13) pp:NaN3851-3851
Publication Date(Web):2011/02/14
DOI:10.1039/C0CC05235C
Ag6L6-type coordination nanotubular structures have been assembled from 6 Ag(I) ions and 6 T-shaped ligands, 4-(3,5-bis(diphenylphosphino)phenyl)pyridine; the nanotubes represent a discrete molecular architecture of a number of polymeric structures assembled from dimeric building blocks.
Co-reporter:Yu-Hao Li, Ji-Jun Jiang, Yan-Zhong Fan, Zhang-Wen Wei, Cheng-Xia Chen, Hui-Juan Yu, Shao-Ping Zheng, Dieter Fenske, Cheng-Yong Su and Mihail Barboiu
Chemical Communications 2016 - vol. 52(Issue 56) pp:NaN8748-8748
Publication Date(Web):2016/06/16
DOI:10.1039/C6CC04420D
Fully structural interconversions between monomeric Pd2L4 and interlocked dimeric Pd4L8 cages have been investigated to elucidate their thermodynamic stability defined by their anion-guest binding behaviours.
Co-reporter:Zhao Zhang, Heini Feng, Lin Liu, Chao Yu, Xingqiang Lü, Xunjin Zhu, Wai-Kwok Wong, Richard A. Jones, Mei Pan and Chengyong Su
Dalton Transactions 2015 - vol. 44(Issue 13) pp:NaN6241-6241
Publication Date(Web):2015/02/19
DOI:10.1039/C5DT00141B
In the series of homo-leptic trinuclear complexes {[Ln3(L)4Cl4(MeOH)(H2O)]·Cl} (Ln = La, 1; Ln = Eu, 2; Ln = Tb, 3 or Ln = Gd, 4) self-assembled from the allyl-modified benzimidazole-type ligand HL (4-allyl-2-(1H-benzo[d]imidazol-2-yl)-6-methoxyphenol) and LnCl3·6H2O, a suitable energy level match endows efficient green luminescence (Φoverall = 72%) of Tb3-arrayed complex 3. The copolymerization between each of these complex monomers 1–4 and CC-containing MMA (methyl methacrylate) or NBE (norbornene) shows that degradative chain transfer of the terminal four flexible allyl groups within restrains their radical polymerization with MMA while it does not hinder their effective ring-opening metathesis polymerization (ROMP) with NBE. Thus, two kinds of PMMA-supported doping hybrid materials 1@PMMA, 2@PMMA, 3@PMMA and 4@PMMA and PNBE-supported metallopolymer-type hybrid materials Poly(NBE-1), Poly(NBE-2), Poly(NBE-3) and Poly(NBE-4) are obtained, respectively. Especially for both 3@PMMA and Poly(NBE-3) with high color-purity characteristic green emission of Tb3+ ions, improved physical properties including significantly enhanced luminescence (Φoverall = 76% or 83%) are observed, and covalent-bonding endows a higher-concentration self-quenching as compared to physical doping.
Co-reporter:Haoliang Liu, Juan Feng, Jianyong Zhang, Philip W. Miller, Liuping Chen and Cheng-Yong Su
Chemical Science (2010-Present) 2015 - vol. 6(Issue 4) pp:NaN2296-2296
Publication Date(Web):2015/02/18
DOI:10.1039/C5SC00314H
A novel dynamic covalent gel strategy is reported to immobilize an asymmetric catalyst within the channels of a microfluidic flow reactor. A layer of a catalytically active Mn–salen dynamic covalent imine gel matrix was coated onto a functionalized capillary. Mn–salen active moiety was incorporated into dynamic covalent imine gel matrix via the reaction of a chiral Mn–salen dialdehyde unit with a tetraamine linker. The catalytic activity of the capillary reactor has been demonstrated in enantioselective kinetic resolution of secondary alcohols.
Co-reporter:Jiewei Liu, Lianfen Chen, Hao Cui, Jianyong Zhang, Li Zhang and Cheng-Yong Su
Chemical Society Reviews 2014 - vol. 43(Issue 16) pp:NaN6061-6061
Publication Date(Web):2014/05/29
DOI:10.1039/C4CS00094C
This review summarizes the use of metal–organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal–organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.
Co-reporter:Lianfen Chen, Tao Yang, Hao Cui, Tao Cai, Li Zhang and Cheng-Yong Su
Journal of Materials Chemistry A 2015 - vol. 3(Issue 40) pp:NaN20209-20209
Publication Date(Web):2015/08/28
DOI:10.1039/C5TA05592J
Self-assembly of dirhodium(II) tetraacetate (Rh2(OAc)4) with a dicarboxylic acid 3,3′-(1,3-phenylenebis(ethyne-2,1-diyl))dibenzoic acid (H2pbeddb) gives rise to a metal–organic cage (MOC) containing Rh–Rh bonds with the formula of [Rh4(pbeddb)4(H2O)2(DMAC)2] (MOC-Rh-1). Single-crystal X-ray diffraction analysis reveals that MOC-Rh-1 shows a lantern-type cage structure, in which a pair of Rh2(CO2)4 paddlewheels is linked by four diacid ligands. The dimensions of the inner cavity of MOC-Rh-1 are 9.5 × 14.8 Å2 (atom-to-atom distances across opposite metal and phenyl groups of pbeddb2−). In the solid phase, the cages are aligned by π–π stacking to form one-dimensional channels (9.5 × 11.1 Å2) through cage windows. Therefore, the crystalline samples of MOC-Rh-1 are porous with the inner and outer cavities of the cages accessible under the heterogeneous condition. MOC-Rh-1 has been fully characterized by EA, TGA, PXRD, IR, UV-vis and XPS measurements. The catalytic tests disclose that activated MOC-Rh-1 is effective in the intramolecular C–H amination of vinyl, dienyl and biaryl azides, leading to the formation of indoles, pyrroles and carbazoles, respectively, and the porous catalyst can be recycled easily and used for at least nine runs without significant loss of activity. In the nine runs, the conversions were in the range of 93–99%, whereas in the tenth run, the conversion was reduced to 78%.
Co-reporter:Qian Zhang, Lisi He, Jun-Min Liu, Wei Wang, Jianyong Zhang and Cheng-Yong Su
Dalton Transactions 2010 - vol. 39(Issue 46) pp:NaN11179-11179
Publication Date(Web):2010/10/21
DOI:10.1039/C0DT00406E
M2L2 type metallacyclic complexes, [Pd2(L1)2Cl4]·1.5CH2Cl2 (1), [Pd2(L1)2Cl4]·2CHCl3 (2), [Pd2(L2)2Cl4]·2CH2Cl2·2CH3CN (3), [Pd2(L2)2Cl4]·2CHCl3·2CH3CN (4) and [Pd2(L3)2Cl4]·CH2Cl2·2CH3CN (5), have been prepared from three semi-rigid benzimidazol or benzotriazol ligands, 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L1), 1,4-bis(5,6-dimethylbenzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L2) and 1,4-bis(benzotriazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L3). All the complexes were structurally characterized by single-crystal X-ray diffraction and the phase purity was confirmed by powder X-ray diffraction (PXRD) measurements. The solution structure of representative complex 1 was studied by 1H NMR titration and ESI mass spectroscopy. The thermal stability and guest-exchange properties of 1, 3 and 4 were investigated, revealing that the Pd2L2 metallacycles can act as a selective receptor for CH2Cl2 or CHCl3 guest molecules. The catalytic activity of 1 in Suzuki–Miyaura coupling reaction was also studied and 1 could be recycled at least 5 times under heterogeneous conditions, indicative of a potential self-supported catalyst.
Co-reporter:Hong-Yan Chen, Dai-Bin Kuang and Cheng-Yong Su
Journal of Materials Chemistry A 2012 - vol. 22(Issue 31) pp:NaN15489-15489
Publication Date(Web):2012/05/28
DOI:10.1039/C2JM32402D
As one of the most promising low cost alternatives to the traditional p–n junction photovoltaic device, the dye-sensitized solar cell (DSSC) has attracted immense attention from academic and industrial researchers in the last two decades. The size, structure and morphology of photoanode materials have been found to show significant influence on the photovoltaic performance of DSSCs. In this feature article, we briefly summarize the synthesis and properties of hierarchically micro/nanostructured semiconductor (TiO2, ZnO, SnO2) photoanode materials involving microspheres and one-dimensional nanostructure, and their photovoltaic performance in DSSCs.
Co-reporter:Qiu-Ping Luo, Bing-Xin Lei, Xiao-Yun Yu, Dai-Bin Kuang and Cheng-Yong Su
Journal of Materials Chemistry A 2011 - vol. 21(Issue 24) pp:NaN8714-8714
Publication Date(Web):2011/05/10
DOI:10.1039/C1JM10871A
Vertically aligned hierarchical ZnO rod-in-tube nano-architecture arrays are produced via a two-step process including an initial hydrothermal reaction followed by ultrasonication growth. The ZnO nanorod arrays grow firstly on FTO glass through a hydrothermal process and then act as templates for the fabrication of rod-in-tube nano-architectures during ultrasonication. The as-prepared ZnO rod-in-tube nano-architectures are assembled by the self-stacking of hexagonal nanorings along with <001> orientation of ZnO nanorod templates. Both hexamethylenetetramine and sodium citrate are found to play key roles in the formation of the novel ZnO rod-in-tube nano-architectures. The power conversion efficiency of dye-sensitized solar cell based on hierarchical ZnO rod-in-tube nano-architectures photoelectrode (0.91%) exhibits a significant improvement (75%) compared to that of ZnO nanorods (0.52%).
Co-reporter:Mei Pan, Xiang-Li Zheng, Yu Liu, Wei-Sheng Liu and Cheng-Yong Su
Dalton Transactions 2009(Issue 12) pp:NaN2169-2169
Publication Date(Web):2009/02/03
DOI:10.1039/B818322H
Six N-substituted NTB ligands (NTB = (tris(benzimidazol-2-ylmethyl)amine), namely, triMeNTB (L1), triEtNTB (L2), triPrNTB (L3), triBuNTB (L4), triAlNTB (L5) and triBzNTB (L6), have been synthesized through replacing the H atoms on the NH groups by methyl, ethyl, npropyl, nbutyl, allyl, and benzyl groups, respectively. Their corresponding Sm3+, Eu3+ and Tb3+ complexes consisting of different anions or secondary ligands have been prepared and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction measurements. Three types of structural models have been obtained: ML2 where two triTNTB ligands wrap around the Ln3+ ion with anions (ClO4− and CF3SO3−) free of coordination, MLA3 where one triRNTB ligand holds the Ln3+ ion with anions (Cl−, NO3− and picrate) participating in coordination, and MLL′3 where one triNTB ligand and three secondary antipyrine ligands coordinate with the Ln3+ ion. The Ln3+ ions in ML2 type complexes are 8-coordinating and display a slightly distorted cubic (LnN8) coordination geometry. The Ln3+ ions in MLA3 and MLL′3 types complexes show two different coordination geometries: one is 7-coordinating (MLA3 with Cl− anion and MLL′3), which can be described as a severely distorted cube short of one corner (LnN4Cl3 or LnN4O3), and the other is 10-coordinating (MLA3 with NO3− and picrate anions) which can be regarded as a severely distorted cube with one corner substituted by a three-atom cap (LnN4O6). The photoluminescent study reveals that the complexes with different Ln3+ ions show a general luminescent intensity tendency of Tb > Eu > Sm. The modification of the NTB molecule by altering R groups tunes the triplet states of the ligands and results in differentiable photophysical properties of the complexes. The anions or secondary ligand also have remarkable effects on the luminescent properties of the complexes.
Co-reporter:Ji-Jun Jang, Lei Li, Tao Yang, Dai-Bin Kuang, Wei Wang and Cheng-Yong Su
Chemical Communications 2009(Issue 17) pp:
Publication Date(Web):
DOI:10.1039/B820831J
Co-reporter:Lei Fu, Yu Liu, Mei Pan, Xiao-Jun Kuang, Cheng Yan, Kang Li, Shi-Chao Wei and Cheng-Yong Su
Journal of Materials Chemistry A 2013 - vol. 1(Issue 30) pp:NaN8580-8580
Publication Date(Web):2013/05/10
DOI:10.1039/C3TA11157A
A microporous coordination framework formed by hydrogen-bonding directed assembly of Cu(II) hexanuclear rings can act as a host for iodine accumulation in an aqueous solution. Various iodine species, I−, I3− or I2, are able to be trapped in the hydrophilic voids of the crystals via a single-crystal-to-single-crystal ion-exchange process. The chemical nature of the iodine species encapsulated inside the coordination framework have been established by single crystal and powder XRD, IR, XPS, EA, TG and iodometric methods. Furthermore, the accumulated iodine species can be easily extracted from the crystals by organic solvents. The kinetics of I3− release from the crystals by extraction with ethanol has been studied.
Co-reporter:Qing-Yuan Yang, Kai Wu, Ji-Jun Jiang, Chien-Wei Hsu, Mei Pan, Jean-Marie Lehn and Cheng-Yong Su
Chemical Communications 2014 - vol. 50(Issue 57) pp:NaN7704-7704
Publication Date(Web):2014/05/30
DOI:10.1039/C4CC01763C
Direct white-light emission was first achieved in a single phase material of a Dy(III) metal–organic framework, which also shows tunable yellow-to-blue photoluminescence upon variation of excitation wavelengths.
Co-reporter:Li-Lin Tan, Hong-Yan Chen, Li-Feng Hao, Yong Shen, Li-Min Xiao, Jun-Min Liu, Dai-Bin Kuang and Cheng-Yong Su
Physical Chemistry Chemical Physics 2013 - vol. 15(Issue 28) pp:NaN11917-11917
Publication Date(Web):2013/05/10
DOI:10.1039/C3CP51633D
Starburst triarylamine-based organic dyes (D1, D2, and D3) have been synthesized. For the three designed dyes, the starburst triarylamine group, thiophene (or 3,4-ethylenedioxythiophene), and cyanoacetic acid take the role of electron donor, π-conjugation bridge, and electron acceptor, respectively. These compounds are characterized by photophysical, electrochemical, and theoretical computational methods. Nanocrystalline TiO2-based dye-sensitized solar cells were fabricated using these molecules as light-harvesting sensitizers. The overall efficiencies of the sensitized cells range from 5.48 to 6.15%. It was found that the introduction of the EDOT group in D3 bathochromically extended the absorption spectra, resulting in a leap in the photovoltaic performance in comparison to D2. Incorporation of a hydrophobic carbazole-containing segment at D2 relative with D1 retarded the electron transfer from TiO2 to the oxidized dye or electrolyte, leading to an increase of electron lifetime.
Co-reporter:Cheng Yan, Kang Li, Shi-Chao Wei, Hai-Ping Wang, Lei Fu, Mei Pan and Cheng-Yong Su
Journal of Materials Chemistry A 2012 - vol. 22(Issue 19) pp:NaN9852-9852
Publication Date(Web):2012/04/13
DOI:10.1039/C2JM00001F
In this paper, we report the design of a new functionalized tripodal ligand triCB-NTB (4,4′,4′′-(2,2′,2′′-nitrilotris(methylene)tris(1H-benzo[d]imidazole-2,1-diyl)tris(methylene))tribenzoic acid) and its assembly of Eu(III) homometallic or Zn(II)-Eu(III) heterometallic lanthanide-based metal–organic frameworks (MOFs). C3 symmetric Eu(III) center is achieved in the homometallic MOF, [Eu(triCB-NTB)]·DMAc·4H2O (1). The C3 axis of the three coordinated imino N atoms on the propeller-extended central triCB-NTB ligand coincides with the C3 axis that directs the three para-methyl carboxylic benzene arms on three surrounding ligands coordinating with the central Eu(III) simultaneously. Therefore, a (6, 3) pattern is formed in the framework with relatively large porosity. In the Zn-Eu heterometallic framework, [EuZn(triCB-NTB)(H2O)(Cl)2]·2DMAc·H2O (2), the N atoms on the triCB-NTB are coordinated with Zn(II) and the carboxylic O atoms are coordinated with Eu(III). A paddle-wheel linked Eu(III)2 cluster is formed and 1D loop-and-chain structure is obtained. Two ligands, two Zn(II) ions and two Eu(III)2 clusters constitute one box-like unit on the loop chain. Due to the non-inversion symmetry imposed on the central Eu(III) and the large polarizability of the ligand, both one photon (OP) luminescence based on the energy transfer from the ligand to Eu3+ and two photon (TP) luminescence based on the hypersensitive transition of the Eu3+ ions are observed in the two lanthanide-based MOFs. This satisfies the urgent needs of multi-mode luminescent lanthanide complex. Simultaneously, N2 gas and selective vapor adsorptions were also detected in the porous structure of complexes 1 and 2 due to their benzene-filled channels. The six-pointed-star like cavities in 1 can let the gas and vapor molecules go in and out smoothly subject to changes in the pressure, while the narrower and more irregular channels in 2 show irreversible adsorption behavior for benzene and cyclohexane vapor molecules in vacuum under room temperature.
Co-reporter:Xiao-Ming Lin, Ting-Ting Li, Lian-Fen Chen, Li Zhang and Cheng-Yong Su
Dalton Transactions 2012 - vol. 41(Issue 34) pp:NaN10429-10429
Publication Date(Web):2012/06/18
DOI:10.1039/C2DT30935A
A microporous Pb(II) metal–organic framework (MOF) [PbL2]·2DMF·6H2O (1) has been assembled from a N-oxide and amide doubly functionalized ligand HL (= N-(4-carboxyphenyl)isonicotinamide 1-oxide). Complex 1 features a three-dimensional (3D) framework possessing one-dimensional (1D) rhombic channels with dimensions of 13 × 13 Å2. The 3D framework is built up from 1D PbO2 chains that link ligands in parallel fashion to construct single-wall channels. When recrystallizing 1 in a DMSO–DMF mixture (3:5 v/v), a new coordination polymer, [PbL2]·DMF·2H2O (2), was obtained. Complex 2 is also a 3D framework containing 1D rectangular channels, but the channel dimensions become reduced in size to 13 × 8 Å2 due to reorganization of the Pb(II) coordination environment. The PbO2 chains in 2 are reformed to link ligands in a double-wall fashion, significantly reducing the channel size. Even though, the guest exchange study indicates that the DMF molecules in 2 could be replaced with benzene molecules when immersing in benzene solvent, showing single-crystal-to-single-crystal (SC–SC) guest exchange in the solid state and leading to a daughter crystal [PbL2]·0.5C6H6·2H2O (2′). Desolvated 1 and 2 display preferential adsorption behaviors of water vapour over CO2 due to the hydrophilic nature of the channels and the strong host–guest interactions. Catalytic tests indicate that desolvated 1 and 2 have size-selective catalytic activity towards the Knoevenagel condensation reaction.
Co-reporter:Bin-Bin Du, Yi-Xuan Zhu, Mei Pan, Mei-Qin Yue, Ya-Jun Hou, Kai Wu, Lu-Yin Zhang, Ling Chen, Shao-Yun Yin, Ya-Nan Fan and Cheng-Yong Su
Chemical Communications 2015 - vol. 51(Issue 63) pp:NaN12536-12536
Publication Date(Web):2015/06/29
DOI:10.1039/C5CC04468E
Direct white-light emission and further a dual-channel readable barcode module in both visible and NIR region was established by single-component homo-metallic Pr(III)-MOF crystals for the first time.
Co-reporter:Lei Fu, Mei Pan, Yan-Hu Li, Hong-Bin Wu, Hai-Ping Wang, Cheng Yan, Kang Li, Shi-Chao Wei, Zi Wang and Cheng-Yong Su
Journal of Materials Chemistry A 2012 - vol. 22(Issue 42) pp:NaN22500-22500
Publication Date(Web):2012/09/04
DOI:10.1039/C2JM34992B
A novel butterfly-like Ir(III) complex is designed, synthesized, and characterized for highly efficient yellow phosphorescent polymer-based light-emitting diodes (PLEDs). The device shows a maximum external quantum efficiency of 19.2%, luminance efficiency of 40 cd A−1 and Commission International de L'Eclairage (CIE) color coordinates of (0.49, 0.50) at J = 1.2 mA cm−2.
Co-reporter:Ling Chen, Shao-Yun Yin, Mei Pan, Kai Wu, Hai-Ping Wang, Ya-Nan Fan and Cheng-Yong Su
Journal of Materials Chemistry A 2016 - vol. 4(Issue 29) pp:NaN6966-6966
Publication Date(Web):2016/06/27
DOI:10.1039/C6TC01308B
A highly fluorescent HPI-based excited-state intramolecular proton transfer (ESIPT) molecule is designed and adopted as a naked-eye colorimetric sensor to distinguish methanol, ethanol and isopropanol vapors. Amplified spontaneous emission was also observed for the C1-form single crystal of the molecule attributed to its intrinsic four-level energy states.
Co-reporter:Shuhai Wang, Yanan Fan, Minqi Chen, Yanyu Xie, Dawei Wang and Cheng-Yong Su
Journal of Materials Chemistry A 2015 - vol. 3(Issue 16) pp:NaN8255-8255
Publication Date(Web):2015/03/18
DOI:10.1039/C5TA00904A
Porous Co–P–Pd nanotube arrays (NTAs) are prepared and used for catalyzing the hydrolysis of alkaline NaBH4 solution to generate H2. Benefiting from the unique porous structure and synergistic effect, the Co–P–Pd NTAs show a maximum hydrogen generation rate of 4216 mL per min per g catalyst and good cyclic stability.
Co-reporter:Jing-Xiang Zhang, Mei Pan and Cheng-Yong Su
Journal of Materials Chemistry A 2017 - vol. 5(Issue 24) pp:NaN4632-4632
Publication Date(Web):2017/05/08
DOI:10.1039/C7TB00702G
The combination of chemotherapy with photodynamic therapy can lead to improved therapeutic efficiencies and reduced side effects compared to conventional chemotherapy. Chlorambucil (CHL) is a DNA alkylating agent, but problems like drug instability, “off-target” binding and in situ monitoring after administration often limit its clinical application. In this regard, we designed a new heteroleptic Ru(II) complex CHL-RuL, bearing a CHL conjugated pendant, which is desired to serve as an image-guided chemo-photodynamic combined theranostic agent. CHL-RuL shows considerable promise as a photosensitizer for two-photon excitation photodynamic therapy: strong and wide UV-Vis absorption bands centered around 400 nm, strong red emission (∼702 nm) with a long lifetime at the microsecond level, moderate singlet oxygen quantum yield, and significant two-photon absorption cross-section (118 GM). More interestingly, this chemical modification affords CHL-RuL greater cellular uptake and remarkable mitochondria accumulation in HeLa cells. Furthermore, CHL-RuL shows a slight selective cytotoxicity toward carcinoma HeLa cells over normal MRC-5 cells. MTT assay results and two-photon scanning cell imaging demonstrate that CHL-RuL exhibits obvious chemo-photodynamic dual action against HeLa cells.
Co-reporter:Pei-Yang Su, Li-Bo Huang, Jun-Min Liu, Yi-Fan Chen, Li-Min Xiao, Dai-Bin Kuang, Marcel Mayor and Cheng-Yong Su
Journal of Materials Chemistry A 2017 - vol. 5(Issue 5) pp:NaN1918-1918
Publication Date(Web):2016/12/19
DOI:10.1039/C6TA09314K
The hydrophobic and conductive polymer poly-N-vinylcarbazole (PVK) has been successfully utilized as a multifunctional interlayer between perovskite and the hole transporting material (HTM) for highly stable and efficient perovskite solar cells (PSCs) for the first time. The very thin PVK interlayer can not only protect the perovskite structure from moisture and degradation, but also modulate the interface to reduce charge recombination and promote hole transportation simultaneously. Benefited by coupling this PVK-protection method with the molecular design of an economical and synthetically facile triazatruxene-based HTM (SP-12) featuring good stability, planarity and hole mobility, a reliable power conversion efficiency of 18.8% has been achieved, which is superior to that using the well-studied spiro-OMeTAD (16.9%), demonstrating a promising fabrication approach to efficient and long-term stable PSCs.
Co-reporter:Yingxia Wang, Hao Cui, Zhang-Wen Wei, Hai-Ping Wang, Li Zhang and Cheng-Yong Su
Chemical Science (2010-Present) 2017 - vol. 8(Issue 1) pp:NaN780-780
Publication Date(Web):2016/09/01
DOI:10.1039/C6SC03288E
An iridium-porphyrin ligand, Ir(TCPP)Cl (TCPP = tetrakis(4-carboxyphenyl)porphyrin), has been utilized to react with HfCl4 to generate a stable Ir(III)-porphyrin metal–organic framework of the formula [(Hf6(μ3-O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3]·solvents (Ir-PMOF-1(Hf)), which possesses two types of open cavities (1.9 × 1.9 × 1.9 and 3.0 × 3.0 × 3.0 nm3) crosslinked through orthogonal channels (1.9 × 1.9 nm2) in three directions. The smaller cavity is surrounded by four catalytic Ir(TCPP)Cl walls to form a confined coordination space as a molecular nanoreactor, while the larger one facilitates reactant/product feeding and release. Therefore, the porous Ir-PMOF-1(Hf) can act as a multi-channel crystalline molecular flask to promote the carbenoid insertion reaction into Si–H bonds, featuring high chemoselectivity towards primary silanes among primary, secondary and tertiary silanes under heterogeneous conditions that are inaccessible by conventional homogeneous catalysts.
