Co-reporter:Qi Tan, Jun Fan, Ruiqi Gao, Rujian He, Tai Wang, Yaomou Zhang, Weiguang Zhang
Talanta 2017 Volume 164() pp:362-367
Publication Date(Web):1 March 2017
DOI:10.1016/j.talanta.2016.08.077
•A highly fast analysis and quantification method for triticonazole racemate by SFC.•Residue analysis of triticonazole enantiomers in some vegetables.•Effects of organic modifier on separation and quantification of triticonazole.•Analysis time through SFC was six-fold shorter than through HPLC.A highly fast analytical method though supercritical fluid chromatography (SFC) has been developed to quantify triticonazole enantiomers in cucumbers and tomatoes. Effects of organic modifier type and concentration on chiral separation and quantification of standard solution as well as matrix-matched standard solutions have been studied in detail. Among three organic modifiers, better separation of triticonazole racemate was achieved with 20% ethanol (v/v). The run time in SFC (ca 3 min) with CO2-ethanol (80:20, v/v) as the mobile phase was six-fold shorter than HPLC analysis (about 18 min). Then, QuEChERS (quick, easy, cheap, effective, rugged and safe) extraction procedure was used for triticonazole in vegetables. The residue analysis method was validated. Good linearity (R2≥0.9988) and recoveries (81.62–106.21%, RSD≤7.30%) for the two enantiomers were achieved. This developed method described herein is convenient and reliable for enantioselective detection of triticonazole in vegetables, which might provide additional information for reliable risk assessment of chiral pesticides.
Co-reporter:Kai Zhang, Song-Liang Cai, Yi-Lun Yan, Zi-Hao He, Hui-Mei Lin, Xiao-Ling Huang, Sheng-Run Zheng, Jun Fan, Wei-Guang Zhang
Journal of Chromatography A 2017 Volume 1519(Volume 1519) pp:
Publication Date(Web):13 October 2017
DOI:10.1016/j.chroma.2017.09.007
•A new hydrazone-linked chiral COF is designed and synthesized.•The hydrazone-linked chiral COF exhibits remarkable chemical stability.•The COF–silica composite is prepared and used as the stationary phase for HPLC.•The column offered good separation of positional isomers and cis-trans isomers.Covalent organic frameworks (COFs), as an emerging class of crystalline porous organic polymers, have great potential for applications in chromatographic separation owning to their fascinating crystalline structures and outstanding properties. However, development of COF materials as novel stationary phases in high performance liquid chromatography (HPLC) is just in its infancy. Herein, we report the design and construction of a new hydrazone-linked chiral COF, termed BtaMth COF, from a chiral hydrazide building block (Mth) and present a one-pot synthetic method for the fabrication of BtaMth@SiO2 composite for HPLC separation of isomers. The as-synthesized BtaMth chiral COF displays good crystallinity, high porosity, as well as excellent chemical stability. Meanwhile, the fabricated HPLC column by using BtaMth@SiO2 composite as the new stationary phase exhibits high resolution performances for the separation of positional isomers including nitrotoluene and nitrochlorobenzene, as well as cis-trans isomers including beta-cypermethrin and metconazole. Additionally, some effects such as the composition of the mobile phase and column temperature for HPLC separations on the BtaMth@SiO2 packed column also have been studied in detail. The successful applications indicate the great potentials of hydrazone-linked chiral COF–silica composite as novel stationary phase for the efficient HPLC separation.
Co-reporter:Song-Liang Cai;Zi-Hao He;Wan-Hua Wu;Fang-Xiu Liu;Xiao-Ling Huang;Sheng-Run Zheng;Jun Fan
CrystEngComm (1999-Present) 2017 vol. 19(Issue 22) pp:3003-3016
Publication Date(Web):2017/06/07
DOI:10.1039/C7CE00568G
Two new imidazole-based dicarboxylate ligands, which are 2-(pyridin-4-ylmethyl)-1H-imidazole-4,5-dicarboxylic acid (H3pPyMIDC) and 2-(pyridin-3-ylmethyl)-1H-imidazole-4,5-dicarboxylic acid (H3mPyMIDC), have been designed and successfully synthesized. Both these multidentate ligands are then used to react with different kinds of alkaline earth metal ions under solvothermal conditions, leading to the construction of a series of new coordination polymers (CPs), namely, [Ba(μ5-HpPyMIDC)(H2O)]n (1), [Sr(μ5-HpPyMIDC)(H2O)]n (2), [Ca2(μ4-HpPyMIDC)2(H2O)2]n (3), {[Ca2(μ3-HpPyMIDC)(μ4-HpPyMIDC)(H2O)2]·H2O}n (4), [Ba(μ5-HmPyMIDC)(H2O)]n (5), {[Mg10(μ3-mPyMIDC)3(μ4-mPyMIDC)3(H2O)21]·SO4·12H2O}n (6) and {[Sr(μ2-H2mPyMIDC)2(DMF)2]n·H2O}n (7). Compounds 1 and 2 are isostructural, exhibiting two-dimensional (2D) network structures with a hexagonal honeycomb (6,3) topology if the corresponding metal ions are seen as 3-connected nodes. Compound 3 displays another type of 2D network, which is built by the connection of μ4-HpPyMIDC ligands and Ca(II) centres. Compound 4 is a binodal (3,4)-connected 3D framework with the Schläfli symbol of (6·82)(65·8). The 2D structure of compound 5 is similar to those of compounds 1 and 2, although different kinds of ligands are employed. Compound 6 exhibits an interesting 3D framework with a pcu topology by considering each unusual heptanuclear magnesium cluster as a 6-connected node. In compound 7, connection of μ2-H2mPyMIDC ligands with Sr(II) ions results in the formation of an uncommon 3D chiral framework containing two different types of 1D helical chains. The present results reveal that both these new imidazole-based dicarboxylate ligands containing flexible pyridinylmethyl groups show versatile coordination abilities and are good candidates for fabricating new CPs. Moreover, the thermogravimetric and solid-state luminescence properties of all the compounds have also been studied.
Co-reporter:Jun Wang;Song-Liang Cai;Kai Zhang;Chao-Jie Li;Ying Feng;Jun Fan;Sheng-Run Zheng
CrystEngComm (1999-Present) 2017 vol. 19(Issue 2) pp:391-391
Publication Date(Web):2017/01/04
DOI:10.1039/C6CE90202B
Correction for ‘Anion- and temperature-dependent assembly, crystal structures and luminescence properties of six new Cd(II) coordination polymers based on 2,3,5,6-tetrakis(2-pyridyl)pyrazine’ by Jun Wang et al., CrystEngComm, 2016, 18, 5164–5176.
Co-reporter:Tao Chen, Jun Fan, Ruiqi Gao, Tai Wang, Ying Yu, Weiguang Zhang
Journal of Chromatography A 2016 Volume 1467() pp:246-254
Publication Date(Web):7 October 2016
DOI:10.1016/j.chroma.2016.07.007
•Chiral separations of metalaxyl by HPLC coupled with four detectors.•Effect of chromatographic conditions on peak area ratio between two enantiomers.•Comparative evaluation of four detectors for quantification of enantiomers.Chiral stationary phase-high performance liquid chromatography coupled with various detectors has been one of most commonly used methods for analysis and separation of chiral compounds over the past decades. Various detectors exhibit different characteristics in qualitative and quantitative studies under different chromatographic conditions. Herein, a comparative evaluation of HPLC coupled with ultraviolet, optical rotation, refractive index, and evaporative light scattering detectors has been conducted for qualitative and quantitative analyses of metalaxyl racemate. Effects of separation conditions on the peak area ratio between two enantiomers, including sample concentration, column temperature, mobile phase composition, as well as flow rate, have been investigated in detail. In addition, the limits of detection, the limits of quantitation, quantitative range and precision for these two enantiomers by using four detectors have been also studied. As indicated, the chromatographic separation conditions have been slight effects on ultraviolet and refractive index detections and the peak area ratio between two enantiomers remains almost unchanged, but the evaporative light scattering detection has been significantly affected by the above-mentioned chromatographic conditions and the corresponding peak area ratios varied greatly. Moreover, the limits of detection, the limits of quantitation, and the quantitative ranges of two enantiomers with UV detection were remarkably lower by 1–2 magnitudes than the others.
Co-reporter:Song-Liang Cai, Sheng-Run Zheng, Jun Fan, Rong-Hua Zeng and Wei-Guang Zhang
CrystEngComm 2016 vol. 18(Issue 7) pp:1174-1183
Publication Date(Web):12 Jan 2016
DOI:10.1039/C5CE02138C
Solvothermal reactions of Co2+ and Mn2+ salts with 2-(trifluoromethyl)-1H-4,5-imidazole dicarboxylic acid (H3TFMIDC) lead to two novel three-dimensional (3D) metal–organic frameworks (MOFs), namely, [Co6(μ3-TFMIDC)4(H2O)12]·15H2O (1) and [(Me2NH2)3][MnII6 MnIII(μ3-TFMIDC)6(H2O)6]·18H2O (2). Single-crystal X-ray diffraction analysis reveals that both of them are based on interesting planar tetranuclear squares [M4(TFMIDC)4] as secondary building units (SBUs). Compound 1 exhibits a unique 3D two-fold interpenetrated network with the diamondoid topology consisting of the tetranuclear square SBUs as 4-connected nodes, while compound 2 features an unusual (6,16)-connected 3D framework based on the novel tetranuclear square SBUs as 16-connected nodes and trivalent manganese ions as 6-connected nodes, representing the first 16-connected MOF utilizing planar tetranuclear square SBUs as building blocks. Our results open up new perspectives to design novel 3D extended MOFs, especially the unique highly connected 3D MOFs by employing planar tetranuclear square SBUs. Moreover, IR spectroscopy, powder X-ray diffraction, thermogravimetric analyses, and a study on the magnetic properties of both compounds, have been also performed.
Co-reporter:Jun Wan, Song-Liang Cai, Kai Zhang, Chao-Jie Li, Ying Feng, Jun Fan, Sheng-Run Zheng and Wei-Guang Zhang
CrystEngComm 2016 vol. 18(Issue 27) pp:5164-5176
Publication Date(Web):17 May 2016
DOI:10.1039/C6CE00853D
Solvothermal reactions of 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz) and sodium azide with different cadmium salts including CdCl2·2.5H2O, Cd(NO3)2 and Cd(CH3COO)2·2H2O at 80 °C produce three new coordination polymers, namely, {[Cd2(N3)2(tppz)Cl2]·2H2O}n (1), [Cd2(N3)2(tppz)(NO3)2]n (2) and {[Cd2(N3)2(tppz)(CH3COO)2]·2H2O}n (3), respectively. Single-crystal X-ray diffraction analysis reveals that the anions of the Cd(II) salts all participate in coordination in compounds 1–3. Compound 1 features an infinite one-dimensional (1D) chain with loops-and-rods topology, compound 2 exhibits a 1D ladder-like chain, while compound 3 possesses a 2D honeycomb-like network structure with (6,3) topology. The low-dimensional structures of compounds 1–3 are further stabilized by diverse supramolecular interactions such as hydrogen bonds and π⋯π stacking. Interestingly, when the temperature is increased to 100 °C, similar reactions of tppz and sodium azide ligands with CdCl2·2.5H2O, Cd(NO3)2 and Cd(CH3COO)2·2H2O lead to three other novel 3D Cd(II) coordination polymers formulated as [Cd3(N3)6(tppz)]n (4), {[Cd2(N3)2(tppz)(NO3)2]·MeOH}n (5) and [Cd4(N3)6(tppz)(CH3COO)2]n (6), respectively. The anions of the Cd(II) salts again take part in coordination in compounds 5 and 6 but disappear in the final structure of 4. Compound 4 displays a rare sxd-type 3D framework with the Schläfli symbol of (33·46·55·6) if each V-shaped trinuclear [Cd3(μ1,1-N3)4] secondary building unit (SBU) is regarded as a 6-connected node. In compound 5, both the Cd1 and Cd2 atoms serve as 3-connected nodes to construct an uncommon binodal (3,3)-connected 3D framework with (6·102)(62·10) topology. Compound 6 contains another type of V-shaped trinuclear [Cd3(μ1,1-N3)2(μ3-CH3COO)] SBU, which acts as a 7-connected node to fabricate a unique uninodal 7-connected 3D framework with a completely new topology of (36·42·510·63). The present results reveal that both anions and temperature play essential roles in the structural and topological diversity of such six new Cd(II) coordination polymers. Moreover, the IR spectra, thermogravimetric analysis curves, and solid-state luminescence properties of all the compounds have been also investigated. Compared with the free tppz ligand, compounds 1–6 exhibit superior luminescence properties with largely enhanced emission, indicating that they may be good candidates for optical materials.
Co-reporter:Sheng-Run Zheng, Li Zhang, Jia-En He, Jun Fan, Wei-Guang Zhang
Inorganic Chemistry Communications 2016 Volume 66() pp:19-23
Publication Date(Web):April 2016
DOI:10.1016/j.inoche.2016.01.019
•Three new CPs based on a bifunctional ligand were constructed.•Compound 1 is a 3D framework composed of 2D coordination layer and helical water chain.•Compound 2 has new pillar-layer 3D structure based on tetranuclear Cd(II) SBUs.Three new coordination polymers, namely, {[Cu2(IPT)(SO4)(OH)(H2O)]·H2O}n (HIPT = 5-(4-(1H-imidazol-1-yl)phenyl)- 1H-tetrazolate, 1), {[Cd2(IPT)(NPA)(OH)]·H2O}n (H2NPA = 5-nitroisophthalic acid, 2), and {[Zn2(IPT)(IDC)(H2O)]·3H2O}n (H3IDC = 1H-imidazole-4,5-dicarboxylic acid, 3), were assembled from a bifunctional organic ligand containing both tetrazole and imidazole groups with/without the aid of carboxylate coligands. Compound 1 possesses 2D structure built by 1D [Cu2(IPT)(SO4)(OH)]n secondary building blocks and IPT− linkers. The 2D networks are linked into 3D supramolecular framework via water chains in helical conformation. Compound 2 displays 3D pillar-layer framework with 2D layers based on tetranuclear Cd(II) SBUs and NPA2 − pillars. Compound 3 exhibits a 3D framework constructed from the interconnection of 1D [Zn-IDC]n chains and binuclear Zn2(IPT)2 rings. The thermal stabilities of porous compound 3 and luminescent properties of compounds 2 and 3 have also been studied in detail. They exhibit intense solid-state fluorescent emissions at room temperature.Three new CPs with interesting structures based on a bifunctional ligand containing both imidazole and tetrazole groups were constructed. Their diverse structures and luminescent properties were studied.
Co-reporter:Song-Liang Cai, Kai Zhang, Jing-Bo Tan, Sha Wang, Sheng-Run Zheng, Jun Fan, Ying Yu, Wei-Guang Zhang, and Yi Liu
ACS Macro Letters 2016 Volume 5(Issue 12) pp:
Publication Date(Web):November 23, 2016
DOI:10.1021/acsmacrolett.6b00805
We report the design and synthesis of an imine-based two-dimensional covalent organic framework (2D COF) with a novel brick-wall topology by judiciously choosing a tritopic T-shaped building block and a ditopic linear linker. Unlike the main body of COF frameworks reported to-date, which consists of higher-symmetry 2D topologies, the unconventional layered brick-wall topology have only been proposed but never been realized experimentally. The brick-wall structure was characterized by powder X-ray diffraction analysis, FT-IR, solid state 13C NMR spectroscopy, nitrogen, and carbon oxide adsorption–desorption measurements as well as theoretical simulations. Our present work opens the door to the design of novel 2D COFs and will broaden the scope of emerging COF materials.
Co-reporter:Shuang-Shuang Hou, Xuan Huang, Jun-Gu Guo, Sheng-Run Zheng, Jing Lei, Jing-Bo Tan, Jun Fan and Wei-Guang Zhang
CrystEngComm 2015 vol. 17(Issue 4) pp:947-959
Publication Date(Web):13 Oct 2014
DOI:10.1039/C4CE01779J
The reactions of Cd(II) salts and 5-(3-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (3-HIPT) resulted in eight new coordination polymers (CPs), namely, {[Cd(3-IPT)2(H2O)2]·H2O}n (1 and 2), {[Cd(3-IPT)2(H2O)2]·2H2O}n (3), [Cd(3-IPT)(H2O)Cl]n (4), [Cd(3-IPT)Cl]n (5), [Cd(3-HIPT)I2]n (6), [Cd(3-IPT)I]n (7), and [Cd(3-HIPT)2]n (8). Single-crystal X-ray analysis revealed that compound 1 is a 1D beaded chain, whereas compounds 2 and 3 are made of 2D networks. Compounds 1–3 are supramolecular isomers; their synthesis can be controlled under different temperatures and concentrations. The results showed that compounds 1 and 3 are the most thermodynamically and kinetically favored products, respectively. The thermodynamic stability of compound 1 may be attributed to the formation of the smallest M2L2 ring in the compound. Compounds 4–7 were obtained at higher Cl−/I− concentrations. Compound 4 is a 2D net composed of 1D [Cd(3-IPT)]n chains and μ2-Cl and μ2-H2O connectors. Compound 5 is a (3,6)-connected 3D framework with rtl topology. Compound 6 possesses a 1D chain with 3-HIPT ligands on both sides. Compound 7 is a 2D (4·82) net. Compound 8, a 3D pcu framework based on trinuclear linear SBUs, was formed when Cd(CF3CO2)2 was introduced at 170 °C. Based on a temperature-changing cycle, compounds 1 and 3 display crystal-to-amorphous-to-crystal phase transitions accompanying the dehydration–rehydration process, whereas compound 2 only displays crystal-to-amorphous phase transition when the temperature is increased and cannot go back to the crystal phase again. Interestingly, solvent-mediated structural transformations were accomplished among the selected compounds. When compounds 2, 3, 6, 7, or 8 were left in a water and NaCl solution at 170 °C, they were partly/fully transformed into compounds 1 and 5, respectively. When compound 5 was recrystallized in water at 120 and 170 °C, it was partly and fully transformed into compounds 2 and 1, respectively. Such transformations were induced by the temperature or an anion. In addition, the thermal stabilities and luminescence properties of selected compounds have also been studied in detail. The complexes exhibit intense solid-state fluorescence emission at room temperature.
Co-reporter:Li Zhang, Jia-Dan Zheng, Yi-Ting Chen, Sheng-Run Zheng, Jun Fan and Wei-Guang Zhang
CrystEngComm 2015 vol. 17(Issue 29) pp:5538-5550
Publication Date(Web):09 Jun 2015
DOI:10.1039/C5CE00767D
Nine new coordination compounds, namely, {[Zn(HDSPTP)2(H2O)4]·6H2O}n (H2DSPTP = 4′-(2,4-disulfophenyl)-4,2′:6′,4′′-terpyridine, (1), [Cd(DSPTP)(H2O)2]n (2), {[Ag(HDSPTP)]·30H2O}n (3), {[Ag(HDSPTP)(H2O)]·3H2O}n (4), [Ag2(DSPTP)]n (5), {[Ag4(DSPTP)2(H2O)3]·2H2O}n (6), [Pb(DSPTP)(H2O)2]n (7), {[Pb(DSPTP)(H2O)3]·3H2O}n (8), and [PbK(DSPTP)(NO3)(H2O)2]·H2O}n (9), were synthesized by introducing a ligand with both terpyridyl and sulfo groups as organic linkers. The reaction of H2DSPTP with Zn(II) salts only resulted in a mononuclear complex (compound 1), in which most donor groups appear uncoordinated, whereas the reaction with Cd(II) salts under similar conditions resulted in a three-dimensional (3D) twofold interpenetrated dia framework (compound 2). The reactions of H2DSPTP with AgCF3CO2 or AgNO3 resulted in compounds 3–6 with different structures: a porous supramolecular framework via interlaced packing of one-dimensional (1D) coordination chains (compound 3), a two-dimensional (6,3) network based on coordination bonds and Ag⋯O interactions (compound 4), a 3D framework based on 1D [Ag2(2-SO3−)2]n secondary building blocks (compound 5), and a twofold interpenetrated framework with a binodal (4,6)-connected fsh topology based on planar tetranuclear SBUs as nodes (compound 6). The reactions of H2DSPTP with Pb(NO3)2 resulted in the following three compounds: a 3D twofold interpenetrated dia framework (complex 7), a twofold interpenetrated (6,3) network (compound 8), and a 3D complicated framework based on tetranuclear SBUs, double-bridge DSPTP2− ligands, and [K(H2O)]+ species (compound 9). The structural diversity is mainly attributed to the rich coordination behaviors of the HDSPTP−/DSPTP2− ligands and the metal center and can be controllably synthesized by altering the metal to ligand ratio, added alkali, and the pH value for the Ag(I) and Pb(II) compounds. Compound 2 exhibits a high thermal stability above 500 °C, undergoes a crystalline–amorphous–crystalline phase transition as temperature is increased from 25 °C to 500 °C, and shows an amorphous–crystalline phase transition when rehydrated. Moreover, the luminescence properties of all the compounds were also investigated.
Co-reporter:Sheng-Run Zheng, Zhen-Zhen Wen, Yin-Yu Chen, Song-Liang Cai, Jun Fan, Wei-Guang Zhang
Inorganic Chemistry Communications 2015 Volume 55() pp:165-168
Publication Date(Web):May 2015
DOI:10.1016/j.inoche.2015.03.035
•Two Ln(III) coordination polymers based on H3PyIDC were successfully synthesized.•Compound 1 displays 3D frameworks with new (3,4)-connected topology.•Compound 2 exhibits a rare (3,4)-connected dmc topology.Two new lanthanide (III) coordination polymers, namely, {[Eu3(μ3-HPyIDC)4]·Cl}n, (1) and {[Tb2(μ3-HPyIDC)2(μ2-Ox) (H2O)2]·4H2O}n (2) (H3PyIDC = 2-(3-Pyridyl)-1H-4, 5-imidazoledicarboxylic acid; Ox = oxalate), were successfully synthesized under hydro(solvo)thermal conditions and structurally characterized. Compound 1 displays a 3D framework with new (3,4)-connected {4.8.10}4{4.84.12}2{42.84} topology built by 3-connected μ3-HPyIDC− nodes and 4-connected metal ions. Compound 2 exhibits a rare (3,4)-connected dmc topology, in which μ3-HPyIDC− anions are 3-connected nodes and metal ions are 4-connected nodes. Moreover, the thermal stabilities and luminescence of compounds 1–2 were also investigated.Two novel three-dimensional Ln(III) coordination frameworks with (3,4)-connected topologies based on H3PyIDC with/without ox auxiliary ligands were successfully obtained.
Co-reporter:Song-Liang Cai, Yue-Biao Zhang, Andrew B. Pun, Bo He, Jinhui Yang, Francesca M. Toma, Ian D. Sharp, Omar M. Yaghi, Jun Fan, Sheng-Run Zheng, Wei-Guang Zhang and Yi Liu
Chemical Science 2014 vol. 5(Issue 12) pp:4693-4700
Publication Date(Web):2014/09/16
DOI:10.1039/C4SC02593H
Despite the high charge-carrier mobility in covalent organic frameworks (COFs), the low intrinsic conductivity and poor solution processability still impose a great challenge for their applications in flexible electronics. We report the growth of oriented thin films of a tetrathiafulvalene-based COF (TTF-COF) and its tunable doping. The porous structure of the crystalline TTF-COF thin film allows the diffusion of dopants such as I2 and tetracyanoquinodimethane (TCNQ) for redox reactions, while the closely packed 2D grid sheets facilitate the cross-layer delocalization of thus-formed TTF radical cations to generate more conductive mixed-valence TTF species, as is verified by UV-vis-NIR and electron paramagnetic resonance spectra. Conductivity as high as 0.28 S m−1 is observed for the doped COF thin films, which is three orders of magnitude higher than that of the pristine film and is among the highest for COF materials.
Co-reporter:Sheng-Run Zheng, Rui-Ling Chen, Tao Xie, Zi-Meng Liu, Xi-Ling Wen, Xue-Yun Chen, Jun Fan and Wei-Guang Zhang
CrystEngComm 2014 vol. 16(Issue 19) pp:4029-4037
Publication Date(Web):08 Nov 2013
DOI:10.1039/C3CE41790E
Five new coordination polymers, [Mg(DSPT)(H2O)2]·2H2O (H2DSPT = 4′-(2,4-disulfophenyl)-2,2′:6′2′′-terpyridine) (1), {[Ca(DSPT)(H2O)2]·1.5H2O}n (2), {[Pb(DSPT)(H2O)]·2H2O}n (3), {[Pb(DSPT)]·0.5H2O}n (4), and {[Pb3(DSPT)3(H2O)]·8H2O}n (5), were prepared under hydrothermal conditions. They are all complexes containing similar M2L2 binuclear metal–terpyridine building units. Complex 1 is a discrete binuclear molecule that extends to 2D layers via O–H⋯O hydrogen bonds between coordinated water and a sulfo group on H2DSPT. Complexes 2 and 3 are 1D coordination chains based on [M2(DSPT)2] ring subunits but are connected by different M–O bonds, and the 1D chains are also further connected by O–H⋯O hydrogen bonds between coordinated water and a sulfo group on H2DSPT to a 2D layer. Complex 4 exhibits a 2D coordination network also based on the [M2(DSPT)2] ring subunits. Complex 5 is a by-product of the synthesis of complex 4 that displays a 1D coordination chain structure containing the same [M2(DSPT)2] ring subunits. Interestingly, the 2D layers described above show identical skeletons when the bond types between [M2(DSPT)2] ring subunits are neglected. The 2D layers in complexes 1–3 can be derived from replacing selected coordination bonds in complex 4 with hydrogen bonds, and such structural diversity is largely dependent on the number of coordinated water molecules around the metal center. Thermogravimetric analyses of 1–4 showed that they were stable at temperatures higher than 500 °C. The luminescent properties of complexes 1–4 were also investigated.
Co-reporter:Sheng-Run Zheng, Rui-Ling Chen, Zi-Meng Liu, Xi-Ling Wen, Tao Xie, Jun Fan and Wei-Guang Zhang
CrystEngComm 2014 vol. 16(Issue 14) pp:2898-2909
Publication Date(Web):05 Dec 2013
DOI:10.1039/C3CE42091D
Reactions of Ln(III) salts with 4′-(2,4-disulfophenyl)-2,2′:6′2′′-terpyridine (H2DSPT) result in five types of coordination polymers, namely, {[Gd(DSPT)(OH)(H2O)2]·4H2O}n (type I, 1), {[Ln(DSPT)(ox)0.5]·H2O}n (type II, Ln = Nd (2), Eu (3), Tb (4), Er (5), Yb (6), Lu (7), ox = oxalate), {[Ln(DSPT)(ox)0.5(H2O)]·4H2O}n (type III, Ln = Yb (8), Lu (9)), {[Ln(DSPT)(pBDC)0.5·(H2O)2]·5H2O}n (type IV, Ln = Yb (10), Lu (11), H2pBDC = 1,4-benzenedicarboxylic acid), and {[Ln(DSPT)(pBDC)0.5·(H2O)2]·5H2O}n (type V, Ln = Dy (12), Er (13)). Type I is a 1D chain built from binuclear Ln2(DSPT)2 building blocks and OH− linkers. Type II is a 2D layer with (4,5)-connected topology constructed by binuclear Ln2(DSPT)2 building blocks and ox− anions. Type III is also a 2D network based on Ln(III), DSPT2−, and ox−, but with (3,4)-connected topology. The ox− anion is generated in situ from carboxylic acid precursor in type II and type III structures. The formation of Lu(III) complexes of type II or type III can be tuned by the addition of different carboxylic precursors. Type IV posseses a 2D layered structure based on the [Ln(DSPT)]n chain connected by pBDC2−. Type V exhibits a 3D framework formed by binuclear [Ln2(SO3)2(COO)2] secondary building blocks and DSPT2− and pBDC2− linkers, resulting in a uninodal 8-connected sqc4 topology. The Nd- and Yb-centered complexes show strong NIR luminescence, whereas the Tb- and Eu-centered complexes exhibit strong luminescence in the visible region at room temperature in both solid state and water emulsions. Their luminescence intensity can be strongly quenched by the addition of diethylchlorophosphonate (DCP), but significantly less influenced by dimethylmethylphosphonate (DMMP), diethylcyanophosphonate (DCNP) and other selected organophosphate, which make this material have a potential application in nerve-agent detection.
Co-reporter:Yi Tan;Jun Fan;Chun Lin;Hongsheng Tu;Shengrun Zheng ;Weiguang Zhang
Journal of Separation Science 2014 Volume 37( Issue 5) pp:488-494
Publication Date(Web):
DOI:10.1002/jssc.201301146
Two new polysaccharide-derived chiral selectors, namely, 6-azido-6-deoxy-3,5-dimethylphenylcarbamoylated amylose and 6-azido-6-deoxy-3,5-dimethylphenyl carbamoylated cellulose, were synthesized under homogeneous conditions and immobilized onto aminized silica gel by the Staudinger reaction, resulting in two new immobilized polysaccharide chiral stationary phases (CSPs). Their enantioseparation performances were investigated under normal-phase mode by HPLC. Among 17 analytes, baseline separations of 12 pairs of enantiomers are achieved on the immobilized cellulose CSP, which demonstrates that this new cellulose material exhibits almost the same enantioseparation performance as the coated cellulose CSP. In addition, the amylose-derived CSP presents limited enantiorecognition ability but certain complementarity with the immobilized and coated cellulose-based materials. Neither metolachlor nor paclitaxel side chain acids are separated on two cellulose-derived CSPs, but effective separations are obtained on the immobilized amylose column.
Co-reporter:Chun Lin, Jun Fan, Wen-na Liu, Yi Tan, Wei-guang Zhang
Journal of Pharmaceutical and Biomedical Analysis 2014 Volume 98() pp:221-227
Publication Date(Web):September 2014
DOI:10.1016/j.jpba.2014.05.032
•Syntheses of two multi-urea-bound cyclodextrin CSPs via the Staudinger reactions.•Complimentary separation of π-acidic/basic phenylcarbamoylated cyclodextrin CSPs.•Effects of organic modifier and mobile phase pH on chiral recognition.•Elution order reversal of enantiomers induced by phenylcarbamate groups.Two new cyclodextrin-derived chiral stationary phases with multiple urea linkages were prepared through the Staudinger reactions between aminopropyl silica gel and cyclodextrin derivatives, namely, heptakis(6-azido-6-deoxy-2,3-di-O-3,5-dimethylphenylcarbamoylated)-β-cyclodextrin and heptakis(6-azido-6-deoxy-2,3-di-O-3,5-dichlorophenylcarbamoylated)-β-cyclodextrin, respectively. HPLC separation behaviors toward 46 chiral analytes have been investigated under multimodal elution. They exhibited good separation performances for these analytes and also showed some complimentary enantioselectivity to each other, due to different electron-donating (methyl)/withdrawing (chlorine) groups in the phenylcarbamate moieties. Among these analytes, aromatic alcohols and N-(2,4-dinitrophenyl)-derived carboxylic acids were better resolved on the π-basic chiral stationary phase than the π-acidic. The proton pump inhibitors, the 5-hydroxytryptamine receptor antagonists, and the analytes with carbonyl groups easily formed stereoselective interactions with the π-acidic chiral stationary phase, further leading to better enantioseparation. Elution order reversal for palonosetron and N-(2,4-dinitrophenyl) glutamine was observed in three chiral stationary phases, probably induced by the difference of phenylcarbamate groups. Moreover, mobile phase effects on retention behaviors of analytes have been studied in detail.
Co-reporter:Shuang-Shuang Hou, Jing-Bo Tan, Zhuo-ying Lian, Dai-Wen Zeng, Tian-Le Huang, Bing-Ru Huang, Sheng-Run Zheng, Jun Fan, Wei-Guang Zhang
Inorganic Chemistry Communications 2014 Volume 47() pp:112-118
Publication Date(Web):September 2014
DOI:10.1016/j.inoche.2014.07.002
•Three new mixed-ligand Zn(II) coordination polymers were constructed.•Compound 1 is a 3D (3,4)-connected framework with InS topology.•Compound 2 has 2D bilayer structure with new 4-nodal (3,4)-connected topology.Reactions of Zn(II) salts, presynthesized 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (HIPT) and various carboxylate ligands result to three new coordination polymers (CPs), namely, [Zn2[(IPT)2(ox)]}n (H2ox = oxalic acid, 1), [Zn2(IPT)2(mNBDC)]n (H2mNBDC = 5-nitroisophthalic acid, 2), and [Zn2(IPT)(CA)(H2O)]n (H3CA = citric acid, 3). Compound 1 can be seen as constructed from 2D [Zn(IPT)]n layers with (6,3) topology and pillared by ox2 −. It is a 3D (3,4)-connected framework with InS topology. Compound 2 has 2D bilayer structure based on 2D [Zn(IPT)]n single layer and mNBDC2 − linkers. Compound 3 is a 3D pillar-layer framework built by Zn–CA bilayers and IPT− pillars. The results showed that the coordination modes, configurations of IPT−, and the structure of carboxylate co-ligands have great influence on the structures of the final network. The choice of carboxylate can decide the result of CPs in Zn–IPT chains/net subunits plus carboxyl linkers or Zn–carboxylate chains/net subunits plus IPT− linkers. The thermal stabilities and luminescent properties of selected compounds have also been studied.Three new Zn(II) CPs with 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (HIPT) and various carboxylate ligands were constructed. They display diverse structures and luminescent properties.
Co-reporter:Zhen Zhen Wen, ShengRun Zheng, SongLiang Cai, JunGu Guo, Xuan Huang, Jun Fan, Wei-Guang Zhang
Inorganic Chemistry Communications 2014 50() pp: 79-83
Publication Date(Web):
DOI:10.1016/j.inoche.2014.10.005
Co-reporter:Chun Lin, Wenna Liu, Jun Fan, Yuekui Wang, Shengrun Zheng, Ran Lin, Hui Zhang, Weiguang Zhang
Journal of Chromatography A 2013 Volume 1283() pp:68-74
Publication Date(Web):29 March 2013
DOI:10.1016/j.chroma.2013.01.087
A novel chiral stationary phase was synthesized by immobilizing heptakis(6-azido-6-deoxy-2,3-di-O-p-chlorophenylcarbamoylated)-β-cyclodextrin onto silica gel surface via Staudinger reaction, and applied in enantiomeric separation of a pair of osmabenzene complexes, {Os[CHC(PPh3)CHC(PPh3)CH](C9H6NO)2}Cl (1), which is the first report for enantioseparation of the chiral-only-at-metal osmabenzene complex till now. The effects of separation conditions including salt additives, organic modifiers, pH values, and column temperature on the retention and resolution of the complex have been investigated in detail. Meanwhile, possible chiral recognition mechanism was presented. Chiral complex 1 was well resolved via semi-preparative chiral HPLC technique under optimization conditions and two pure enantiomers were further characterized by analytical HPLC, NMR spectra and solution circular dichroism (CD) spectra, respectively. Furthermore, absolute configuration of the enantiomer was confirmed by theoretical investigation of CD spectra.Highlights► Synthesis of a novel CD-based CSP with multi-urea linkage via Staudinger reaction. ► Separation of a chiral-only-at-metal osmabenzene complex on MCDP column firstly. ► Effect of chromatographic conditions. ► Configuration of enantiomer determined by theoretical calculation of CD spectra.
Co-reporter:Zhi-Li Fang, Sheng-Run Zheng, Jing-Bo Tan, Song-Liang Cai, Jun Fan, Xia Yan, Wei-Guang Zhang
Journal of Chromatography A 2013 Volume 1285() pp:132-138
Publication Date(Web):12 April 2013
DOI:10.1016/j.chroma.2013.02.024
In this work, a tubular metal–organic framework, MOF-CJ3, with a large one-dimensional channel was chosen as stationary phase to prepare a capillary gas chromatographic column via a verified dynamic coating procedure. The column offered good separations of linear and branched alkanes, as well as aromatic positional isomers (ethylbenzene, xylene, cresol, hydroquinone, dichlorobenzene, bromobenzonitrile, chloronitrobenzene, and nitrotoluene) based on a combination of host–guest interactions and adsorption effects. Elution sequence of most of the analytes followed an increasing order of their boiling points, except for the separation of n-heptanes/isooctane, cresol, and hydroquinone isomers. Separation behavior of the column upon different organic substances may be related to the tubular pore structure of MOF-CJ3, in which the van der Waals forces between the alkanes and the hydrophobic inner surfaces might have great effect on separation of n-heptanes and isooctane, whereas the separation of cresol and hydroquinone isomers were affected by (OH⋯O) hydrogen bonds formed between the analytes and the 1,3,5-benzenetricarboxylate ligands on the pore wall. The effects of temperature on separation of aromatic positional isomers were investigated to elucidate entropy and enthalpy controlling of the separation process.Highlights► MOF-CJ3 was chosen as a stationary phase to prepare a capillary GC column. ► The column offered good separation of linear and branched alkanes. ► The column offered good separation of aromatic positional isomers.
Co-reporter:Rui-Ling Chen, Xue-Yun Chen, Sheng-Run Zheng, Jun Fan, and Wei-Guang Zhang
Crystal Growth & Design 2013 Volume 13(Issue 10) pp:4428-4434
Publication Date(Web):September 4, 2013
DOI:10.1021/cg400926q
Four new 4d–4f heterometallic coordination polymers, namely, {[LnAg(DSPT)(mBDC)(H2O)2]·H2O}n [Ln = Sm, (1); Ln = Er, (2); H2DSPT = 4′-(2,4-disulfophenyl)-2,2′:6′2″-terpyridine); H2mBDC = 1,3-benzenedicarboxylic acid], {[CeAg(DPST)(mBDC)(H2O)2]·H2O}n (3), and {[TbAg3(DPST)2(INC)2(H2O)]}n [HINC = isonicotinic acid, (4)], have been successfully synthesized under hydrothermal conditions and structurally characterized. The four components, including Ln(III) ions, Ag(I) ions, and the two organic ligands, are successfully incorporated into a single framework. They are all heterometallic complexes based on two kinds of molecular building blocks (MBBs), the Ag2(DSPT)2 ring (MBB I) and Ln2(COO)2 dimeric unit (MBB II). Complexes 1 and 2 are isostructural and exhibit a 2D network constructed by MBBs I and II, and further linked by Ag···π interactions to a 3D supramolecular framework. Complexes 3 and 4 are 3D frameworks with sqc-21 and sqc-495 topologies by considering MBB I and II as nodes and coordination bonds/Ag···O interactions as linkers. Complexes 1–4 represent rare examples of 4d–4f coordination polymers containing two kinds of organic ligands. Moreover, thermal gravimetric analysis and luminescence properties studies of selected complexes were also investigated.
Co-reporter:Zhen-Zhen Wen, Xi-Ling Wen, Song-Liang Cai, Sheng-Run Zheng, Jun Fan and Wei-Guang Zhang
CrystEngComm 2013 vol. 15(Issue 26) pp:5359-5367
Publication Date(Web):01 May 2013
DOI:10.1039/C3CE26817A
The reaction of a new ligand, N,N′-(5,7-dihydro-1,3,5,7-tetraoxobenzo[1,2-c:4,5-c′]dipyrrole-2,6(1H,3H)-diyl)bis-(9CI)-3-pyrazinecarboxamide (L), with CuCl2·2H2O, CuI, or Cu(ClO4)·2H2O yields five coordination polymers. Among these polymers are three new coordination polymers, [CuII2(μ3-pzc)2(μ1-Cl)2]n (1), [CuICuII(μ2-pzc)2(μ2-Cl)(H2O)]n (2a), and {[CuI2CuII(μ2-pzc)2(μ3-I)2(H2O)]·H2O}n (3), as well as two previously reported coordination compounds, [CuICuII(μ2-pzc)2(μ2-Cl)(H2O)]n (2b) and [CuII(pzc)2] (4), in which 2-pyrazinecarboxylate (Hpzc) was obtained from in situ hydrolysis of the L ligand. Compound 1 is a two-dimensional (2D) double-layer structure, which can be viewed as a binodal (3,3)-connected network with the Schläfli symbol of (62·10) (6·102). Compounds 2a and 2b are two supramolecular isomers, both of them are (4,4) nets in topological view but showing different packing modes. Compound 3 has a 3D open framework constructed from the linkages of 1D sawtooth chains of iodide copper(I) clusters with [CuII(μ2-pzc)] subunits. Compound 4 is a mononuclear complex. Interestingly, except for compounds 2b and 4, all the other compounds cannot be directly synthesized using Hpzc and the corresponding Cu ions as initial reactants under the same reaction conditions. This finding indicates that the structural diversity of this system is tuned by the in situ hydrolysis reactions.
Co-reporter:Qiuyun Wang;Yajin Xiong;Baozhu Lu;Jun Fan;Sheng Zhang;Shengrun Zheng;Weiguang Zhang
Journal of Separation Science 2013 Volume 36( Issue 8) pp:1343-1348
Publication Date(Web):
DOI:10.1002/jssc.201201165
N-(2,4-dinitrophenyl)-proline and N-(2,4-dinitrophenyl)-serine were enantiomerically resolved on the BSA chiral stationary phase by HPLC in reversed-phase mode. Effects of chromatographic conditions on enantioseparation and elution order have been investigated in detail. For these two samples, reversal of enantiomer elution order was observed by changing buffer pH, the content of acetonitrile, or alcohol modifiers in mobile phase, which is firstly reported in the BSA chiral stationary phase studies. More interestingly, combined effect between buffer pH and the content of acetonitrile was also observed. In addition, coelution range of enantiomers varied along with the content of acetonitrile in mobile phase.
Co-reporter:ZhiLi Fang;WenCui Su;WeiGuang Zhang;Yan Xu;YaJin Xiong;MiaoLi Luo;Jun Fan;Xia Yin
Journal of Molecular Recognition 2013 Volume 26( Issue 4) pp:161-164
Publication Date(Web):
DOI:10.1002/jmr.2247
The chiral discrimination studies of biological system are theoretically and practically significant for the development of chiral drugs and life science. Our work has embarked upon the interaction between serum albumin (SA) (including human SA and bovine SA), R,S-1-(4-methoxyphenyl)ethylamine, and R,S-1-(3-methoxyphenyl)ethylamine. The formation of intermediate transition state, binding sites, and chiral discrimination ability can be investigated by ultraviolet-visible spectra and fluorescence spectra. Moreover, both the changes of hydrophobic microenvironment and energy transfer can be detected by synchronous fluorescence spectra and fluorescence lifetime. Copyright © 2013 John Wiley & Sons, Ltd.
Co-reporter:Jing-Bo Tan, Xue-Yun Chen, Jun Fan, Sheng-Run Zheng, Wei-Guang Zhang
Inorganic Chemistry Communications 2013 Volume 31() pp:49-53
Publication Date(Web):May 2013
DOI:10.1016/j.inoche.2013.02.017
•Three new complexes were obtained via in situ reactions from the same precursor.•These in situ reactions may be directed by metal ions.•Complexes 1–2 show 3D chiral supramolecular frameworks based on 41 helical chains.Three new coordination polymers, [Co(HBit)2]n (1), [Mn(HBit)2]n (2) (H2Bit = 2-((1H-tetrazol-5-yl)methyl)-1H-benzo[d]imidazole), and [CdCl(MBi)(HMBi)]n (3), (HMBi = 2-methyl-1H-benzo-[d]imidazole), have been hydrothermally synthesized via in situ ligand reaction. Compounds 1 and 2 are isomorphous and display interesting 3D chiral supramolecular frameworks constructed from one-dimensional 41 helical chains. Complex 3 possesses a one-dimensional coordination chain, which is further connected to a 2D layer by intermolecular hydrogen bonds. More interestingly, both H2Bit and HMBi ligands are in situ generated from the same precursor, 2-(1H-benzo[d]imidazol-2-yl)-acetonitrile, and the formation may depend on the kind of metal ion. Furthermore, the solid-state luminescence of complex 3 was investigated at room temperature.Three new coordination polymers were obtained by using in situ reaction from the same precursor.
Co-reporter:Qiu-Yun Wang;Ya-Jin Xiong;Bao-Zhu Lu;Jun Fan;Sheng-Run Zheng
Chirality 2013 Volume 25( Issue 9) pp:487-492
Publication Date(Web):
DOI:10.1002/chir.22163
ABSTRACT
Twelve chiral compounds were enantiomerically resolved on bovine serum albumin chiral stationary phase (BSA-CSP) by high-performance liquid chromatography (HPLC) in reversed-phase modes. Chromatographic conditions such as mobile phase pH, the percentage of organic modifier, and concentration of analyte were optimized for separation of enantiomers. For N-(2, 4-dinitrophenyl)-serine (DNP-ser), the retention factors (k) greatly increase from 0.81 to 6.23 as the pH decreasing from 7.21 to 5.14, and the resolution factor (Rs) exhibited a similar increasing trend (from 0 to 1.34). More interestingly, the retention factors for N-(2, 4-dinitrophenyl)-proline (DNP-pro) decrease along with increasing 1-propanol in mobile phase (3%, 5%, 7% and 9% by volume), whereas the resolution factor shows an upward trend (from 0.96 to 2.04). Moreover, chiral recognition mechanisms for chiral analytes were further investigated through thermodynamic methods. Chirality 25:487–492, 2013. © 2013 Wiley Periodicals, Inc.
Co-reporter:Zhi Zhang, Jun Fan, Jianmei Yu, Shengrun Zheng, Wenjing Chen, Heguo Li, Zhijun Wang, and Weiguang Zhang
ACS Applied Materials & Interfaces 2012 Volume 4(Issue 2) pp:944
Publication Date(Web):January 18, 2012
DOI:10.1021/am201603n
A series of copolymers, namely, poly (N, N-dimethylaminoethyl methacrylate)/polyvinyl alcohol (PDMAEMA/PVA), have been obtained through emulsion polymerization. Then, a synthetic copolymer (PDMAEMA/PVA)-coated quartz crystal microbalance sensor (PC-QCM) has been developed to apply in evaluating the interactions between the copolymers and three chemical warfare agent (CWA) simulants, such as diethyl chlorophosphate (DCP), 2,2′-dichlorodiethyl ether (DCE), and dimethyl methylphosphonate (DMMP). The results from the QCM measurements indicate that the PDMAEMA/PVA copolymers not only directly degradate sarin simulants (DCP and DMMP), but also show obvious absorption in mustard gas simulant (DCE). In addition, the mass of degraded DCP by the copolymer is calculated on the basis of resonance frequency shifts (Δf) of quartz crystal in the QCM sensor, which may be applied to quantitatively evaluate the reactivity of PDMAEMA/PVA copolymers. Furthermore, the fluorescence of PDMAEMA/PVA copolymers in DMSO solution gradually quenched with the addition of DCP solution, which can be explained that the reactions take place between DCP and reactive groups of PDMAEMA/PVA copolymers. Thus, this PDMAEMA/PVA membrane may be a good candidate for the application in chemical warfare protective materials, and this new PC-QCM technique shows potential application in the rapid, real-time, and sensitive detection of the chemical warfare agents and hazardous chemicals.Keywords: chemical warfare agent simulants; copolymer-coated QCM sensor; degradation; fluorescence; PDMAEMA/PVA;
Co-reporter:Song-Liang Cai, Sheng-Run Zheng, Zhen-Zhen Wen, Jun Fan, and Wei-Guang Zhang
Crystal Growth & Design 2012 Volume 12(Issue 5) pp:2355-2361
Publication Date(Web):March 29, 2012
DOI:10.1021/cg3000203
Three kinds of new coordination polymers, [Mn(μ3-HPyIDC)(H2O)]n (1a and 1b), {[Cd3(μ4-PyIDC)2(H2O)4]·H2O}n (2), and [Ca(μ4-HPyIDC)(H2O)]n (3a and 3b), were synthesized from the solvothermal reactions of 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid (H3PyIDC) with the corresponding metal salts. Crystal structure analysis showed that all coordination polymers were based on an analogical chiral two-dimensional (2D) secondary building unit (SBU) containing helical chains. The chirality of the 2D SBU was transferred to neighboring 2D SBUs via hydrogen bonds and coordination bonds in 1 and 3, respectively, resulting in two homochiral frameworks. When opposite chirality was transferred between neighboring 2D SBUs via Cd(II) ions, an achiral framework was generated, resulting in 2D nets packed in alternating P and M chirality in compound 2. Furthermore, compounds 1, 2, and 3 feature 2D (82·10), 3D (62·82)(62·82·102), and cds network topologies, respectively. Circular dichroism (CD) measurements also confirmed that the resulting crystals of 1 and 3 are racemic mixtures. Compounds 2 and 3 showed strong fluorescent emissions at room temperature.
Co-reporter:Song-Liang Cai, Sheng-Run Zheng, Zhen-Zhen Wen, Jun Fan, Ning Wang, and Wei-Guang Zhang
Crystal Growth & Design 2012 Volume 12(Issue 9) pp:4441
Publication Date(Web):June 26, 2012
DOI:10.1021/cg300613t
Two types of new d–f heterometallic coordination frameworks, [Ln2M(μ3-HPyIDC)2(ox)2(H2O)4]·4H2O [Ln = Sm, M = Co (1); Ln = Sm, M = Fe (2); Ln = Eu, M = Co (3); Ln = Eu, M = Fe (4); Ln = Gd, M = Co (5); H3PyIDC = 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid; ox = oxalate] for type I and [Ln2Ag3(μ5-PyIDC)(μ6-PyIDC)(μ2-OH)(ox)(H2O)2] [Ln = Sm (6); Gd (7); Tb (8); Dy (9)] for type II, were prepared under hydrothermal conditions and structurally characterized. Complexes 1–5 are isostructural, exhibiting three-dimensional (3D) heterometallic networks with pcu topology based on the linkages of two-dimensional (2D) lanthanide–oxalate layers and pillar-like M(HPyIDC)2 (M = Fe, Co) subunits. Complexes 6–9 are also isomorphous and display another type of 3D heterometallic coordination framework built through the connections of 2D lanthanide–oxalate layers and one-dimensional (1D) Ag2(PyIDC)2 chains. Interestingly, the oxalate ligands in complexes 6–9 are produced by the in situ decarboxylation of the H3PyIDC ligand in the presence of 4,4′-bipyridine (4,4′-bpy). The photoluminescence, thermal stabilities, and magnetic properties of the selected complexes were also investigated.
Co-reporter:Song-Liang Cai, Sheng-Run Zheng, Zhen-Zhen Wen, Jun Fan, and Wei-Guang Zhang
Crystal Growth & Design 2012 Volume 12(Issue 11) pp:5737
Publication Date(Web):October 1, 2012
DOI:10.1021/cg301256g
A series of new three-dimensional (3D) d–f heterometallic coordination polymers, namely, [LnM(μ5-PyIDC)(μ2-INIC)(μ3-INIC)]·xH2O [Ln = Sm, M = Co, x = 3 (1); Ln = Sm, M = Ni, x = 1 (2); Ln = Eu, M = Co, x = 3 (3); Ln = Eu, M = Cd, x = 3 (4); Ln = Eu, M = Zn, x = 3 (5); Ln = Gd, M = Co, x = 3 (6); Ln = Gd, M = Cd, x = 3 (7); Ln = Tb, M = Co, x = 3 (8); Ln = Tb, M = Cd, x = 2 (9); Ln = Tb, M = Zn, x = 3 (10); H3PyIDC = 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid; HINIC = isonicotinic acid], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are isostructural and exhibit novel 3D pillar-layered coordination frameworks constructed by the linkages of 2D heterometallic layers and INIC– pillars. Topological analysis indicates that those complexes possess a rare uninodal 10-connected bct topology based on planar hexanuclear heterometallic [Ln2M4(PyIDC)2] second building units. To the best of our knowledge, complexes 1–10 represent examples of 3D lanthanide–transition heterometal–organic coordination polymers with highly connected bct networks. Moreover, the luminescence properties of complexes 3–5 and 7–10 and the magnetic properties of 6–8 were also investigated.
Co-reporter:Song-Liang Cai, Sheng-Run Zheng, Zhen-Zhen Wen, Jun Fan and Wei-Guang Zhang
CrystEngComm 2012 vol. 14(Issue 23) pp:8236-8243
Publication Date(Web):11 Sep 2012
DOI:10.1039/C2CE25803J
Four three-dimensional (3D) Ln(III)–Zn(II) heterometallic coordination polymers, {[LnZn6(μ4-mPyIDC)4Cl2(H2O)6]·Cl}n [Ln = Sm (1), Eu (2), Tb (3); H3mPyIDC = 2-(pyridine-3-yl)-1H-4, 5-imidazoledicarboxylic acid], and {[LnZn(μ5-pPyIDC)(μ2-SO4)(H2O)3]·3H2O}n [Ln = Tb (4); H3pPyIDC = 2-(pyridine-4-yl)-1H-4,5-imidazoledicarboxylic acid], were prepared under hydrothermal conditions. Isostructural complexes 1–3 were constructed using 1D [Zn3(mPyIDC)2Cl(H2O)3]n chains in a plywood-like packing mode jointed by Ln(III) ions. These compounds display unusual trinodal (3,4)-connected 3D networks with a point symbol of (4·62)4(4·63·82)4(62·82·112). Complex 4 has a highly connected framework with (36·422·516·6) network topology based on a rare planar heterometallic hexanuclear [Tb2Zn4(pPyIDC)2] secondary building block. The luminescent properties of complexes 2–4 were also investigated.
Co-reporter:Song-Liang Cai, Mei Pan, Sheng-Run Zheng, Jing-Bo Tan, Jun Fan and Wei-Guang Zhang
CrystEngComm 2012 vol. 14(Issue 6) pp:2308-2315
Publication Date(Web):30 Jan 2012
DOI:10.1039/C2CE06129E
Three new Cd(II) coordination polymers with 1H-imidazole-4-carboxylic acid (Himc), [Cd(Himc)2(H2O)]n (1), [Cd(Himc)2]n (2) and [Cd2(Himc)2(SO4)(H2O)2]n (3) were perpared by solvothermal reactions and structurally characterized, which all comprised metal–negative ligand systems. Compound 1 exhibit a 1D zigzag chain; compound 2 features a 3D diamondoid work; while compound 3 possesses a 2D layer structure consisting of rhomboid grids. When 1 or 2 was left in a water/ethanolic solution of Na2SO4, their 1D or 3D framework was transformed into a 2D framework of 3. All compounds also displayed structure-related photoluminescent properties in the solid state.
Co-reporter:Sheng-Run Zheng, Song-Liang Cai, Jing-Bo Tan, Jun Fan and Wei-Guang Zhang
CrystEngComm 2012 vol. 14(Issue 19) pp:6241-6245
Publication Date(Web):26 Jun 2012
DOI:10.1039/C2CE25428J
A pair of chiral coordination polymers, [Zn(HPyIDC)]n (1a and 1b, H3PyIDC = 2-(pyridin-3-yl)-1H-imidazole-4,5-dicarboxylate), were assembled from an achiral precursor, H3PyIDC and Zn(II) ions via spontaneous resolution under solvothermal conditions. Crystal structure analysis showed that they are chiral three-dimensional (3D) coordination polymers based on the interconnection of six types of one-dimensional (1D) helical chains. They exhibit an intrinsic chiral (10,3)-a network. The chirality comes from both the stereogenic five-coordinate Zn(II) ions and the axially chiral ligands. Solid-state circular dichroism (CD) spectra measurements confirmed the occurrence of spontaneous resolution of [Zn(HPyIDC)]n and demonstrated that the resulting crystal of [Zn(HPyIDC)]n is a racemic mixture. Compound 1 showed strong fluorescence emission at room temperature.
Co-reporter:Song-Liang Cai, Sheng-Run Zheng, Zhen-Zhen Wen, Jun Fan, and Wei-Guang Zhang
Crystal Growth & Design 2012 Volume 12(Issue 7) pp:3575-3582
Publication Date(Web):May 9, 2012
DOI:10.1021/cg3004068
Four novel three-dimensional (3D) barium–organic coordination polymers formulated as [Ba(μ5-H2hmIDC)(μ2-H2O)]n (1), [Ba(μ3-H3hmIDC)2(μ1-H2O)]n (2), [Ba(μ5-H2hmIDC)(μ2-O2)0.5]n (3), and [Ba(μ3-H3hmIDC)(μ4-H3hmIDC)]n (4) were synthesized under the solvothermal conditions of 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid (H4hmIDC) with BaCl2·2H2O using a combination of water or dimethyl formamide (DMF) with various alcohol solvents (methanol, ethanol, n-propanol, isopropanol, and n-butanol). Complex 1 is a 3D framework based on two-dimensional secondary building units (SBUs) and μ5-H2hmIDC2– pillars. This complex contains a unique alb network topology with the Schläfli symbol (45·6)2(410·614·84). Complex 2 is a (3,10)-connected framework with binuclear [Ba2(COO)2] SBUs as 10-connected nodes and two types of μ3-H2hmIDC2– ligands as 3-connected nodes. Complex 3 is a 3D framework formed with one-dimensional (1D) SBUs and μ5-H2hmIDC linkers, wherein the unprecedented oxygen molecules are coordinated using a linear-μ-η1:η1-peroxo fashion, showing (5,6)-connected network topology with the Schläfli symbol (46·53·6)(46·54·65). Complex 4 is a 3D framework based on 1D SBUs with μ3-H3hmIDC and μ4-H3hmIDC as linkers. This complex exhibits a trinodal (3,4,7)-connected 3D framework with the Schläfli symbol (42·6)(43·63)(48·611·82). The results revealed that the alcohol solvent plays a subtle yet essential role in the crystallization and construction of Ba(II)-organic coordination frameworks with diverse 3D structures, although these alcohol molecules do not appear in the frameworks.
Co-reporter:Song-Liang Cai, Sheng-Run Zheng, Mei Pan, Jing-Bo Tan, Jun Fan and Wei-Guang Zhang
CrystEngComm 2012 vol. 14(Issue 4) pp:1193-1196
Publication Date(Web):14 Dec 2011
DOI:10.1039/C2CE06378F
An unprecedented trinodal (3,4,14)-connected 3D metal–organic framework formed by planar octanuclear lead(II) clusters as 14-connected nodes and 2-(Pyridin-3-yl)-1H-imidazole-4,5-dicarboxylate ligands as 3- and 4-connected nodes has been hydrothermally made. It provides a novel topological structure of metal–organic frameworks.
Co-reporter:ShengRun Zheng, SongLiang Cai, JingBo Tan, Jun Fan, Wei-Guang Zhang
Inorganic Chemistry Communications 2012 Volume 21() pp:100-103
Publication Date(Web):July 2012
DOI:10.1016/j.inoche.2012.04.023
Two new cadmium(II) coordination polymers, namely, {[Cd5Cl2(HBIP)4(BIP)2]·4DMF}n (1) and [Cd3(HBIP)2(BIP)2]n (2), were synthesized from the solvothermal reactions of CdCl2·2.5H2O with 3-(1H-benzimidazol-2-yl) propanoic acid (H2BIP) under different solvent atmospheres. Both the complexes were characterized via elemental analysis, infrared spectra, powder X-ray diffraction, thermogravimetric analysis, and single-crystal X-ray diffraction analysis. Complex 1 exhibits a distinct (4,4) network constructed from the linkage of the N atoms of the μ3-BIP2 − ligands and the infinite pentanuclear secondary building units. Complex 2 presents an interesting onedimensional structure with helical character, composed of four helical chains weaving together in two reverse orientations. Furthermore, the solvent may play a subtle and important role in the assembly procedure. Thermogravimetric analyses show that 2 is stable up to 400 °C. The study of luminescence properties reveals that these complexes exhibit intense, large red-shift emissions in the visible region at room temperature.Two new cadmium(II) coordination polymers based on 3-(1H-benzimidazol-2-yl) propanoic acid (H2BIP) were synthesized under different solvent atmospheres. Moreover, photoluminescent properties and thermal behaviors of both complexes were investigated.Highlights► Two Cd(II) coordination polymers have been obtained using different solvents. ► Complex 1 exhibits a (4,4) network constructed from linear finite pentanuclear cadmium SBUs. ► Complex 2 is a 1D chain with interesting helical character. ► Complexes 1 and 2 exhibit intense, large red-shift emissions in the visible region.
Co-reporter:Xia Yin, Tian-Tian Xiao, Jun Fan, Sheng-Run Zheng, Ning Wang, Song-Liang Cai, Jing-Bo Tan, Wei-Guang Zhang
Inorganic Chemistry Communications 2012 Volume 22() pp:93-97
Publication Date(Web):August 2012
DOI:10.1016/j.inoche.2012.05.031
Two new Mn(II) coordination polymers, namely, [Mn(Haip)2(H2O)2] (1), and [Mn2(aip)2(bpy)]·3H2O (2) were obtained under hydrothermal conditions (aip = 5-aminoisophthalate; bpy = 2, 2′-bipyridine). Compound 1 features a 1D loop-like chain structure, and complex 2 possesses an interesting (3, 5)-connected 2-nodal 3D architecture with the Schläfli symbol of (4.62)(4.67.82), which is constructed from helical chains. Coordination modes of H2aip molecules and coligands have significant effect on the structures of the resulting complexes. Moreover, variable-temperature magnetic susceptibility measurement of complex 2 exhibits antiferromagnetic interactions between nearest Mn(II) ions with J = − 0.88(5) cm− 1 and g = 2.04(3).Two complexes possess a 1D chain and a (3, 5)-connected 2-nodal 3D architecture, respectively. Variable-temperature magnetic susceptibility measurement of compound 2 shows antiferromagnetic interactions between nearest Mn(II) ions.Highlights► Two complexes with different topologies are obtained via hydrothermal reactions. ► Complex 2 was constructed by connection of dinuclear Mn(II) building blocks. ► Coligand and coordination modes of aip affected on structures of two complexes. ► Complex 2 exhibits antiferromagnetic interactions between nearest Mn(II) ions.
Co-reporter:Wen-Jing Chen;Sheng Zhang;Jun Fan;Xia Yin;Sheng-Run Zheng;Wen-Cui Su;Zhi Zhang;Tao Hong
Chirality 2012 Volume 24( Issue 10) pp:804-809
Publication Date(Web):
DOI:10.1002/chir.22074
ABSTRACT
Quartz crystal microbalance (QCM) biosensor was used for the chiral recognition of five pairs of enantiomers by using goat serum albumin (GSA) and rabbit serum albumin (RbSA) as chiral selectors. Serum albumin (SA) was immobilized on the QCM through the self-assembled monolayer technique, and the surface concentration of GSA and RbSA were 8.8 × 10−12 mol cm−2 and 1.2 × 10−11 mol cm−2, respectively. The QCM biosensors showed excellent sensitivity and selectivity. Meanwhile, the chiral recognition of SA sensors was quite species dependent. There were differences between GSA and RbSA sensors in the ability and the preference of chiral recognition. To R,S-1,2,3,4-tetrahydro-1-naphthylamine (R,S-1-TNA), R,S-1-(4-methoxyphenyl)ethylamine (R,S-4-MPEA), and R,S-1-(3-methoxyphenyl)ethylamine (R,S-3-MPEA), the preference of the stereoselective SA-drug binding of the two kinds of SA sensors were consistent. However, to R,S-2-octanol (R, S-2-OT) and R,S-methyl lactate (R,S-MEL), the two kinds of SA sensors had opposite chiral recognition preference. Moreover, the interactions of SA and the five pairs of enantiomers have been further investigated through ultraviolet (UV) and fluorescent (FL) spectra. The UV/FL results were in accordance with the consequence of QCM. Chirality 24:804–809, 2012. © 2012 Wiley Periodicals, Inc.
Co-reporter:Sheng-Run Zheng, Song-Liang Cai, Zhen-Zhen Wen, Jun Fan, Wei-Guang Zhang
Polyhedron 2012 Volume 38(Issue 1) pp:190-197
Publication Date(Web):11 May 2012
DOI:10.1016/j.poly.2012.03.008
The reactions of 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid (H3PyIDC) with different main group metal ions affords five coordination polymers, namely [Ca(HPyIDC)(H2O)2]n (1), [Ba(H3PyIDC)2Cl2]n (2), [Pb(H2PyIDC)2(H2O)2]n (3), {[Mg3(HPyIDC)2(H2O)10]·Cl2}n (4) and {[Mg(HPyIDC)(H2O)]·CH3OH}n (5). Both complexes 1 and 2 are one-dimensional chain structures, but with different connection modes. Complex 1 is constructed by alternate bridges of Ca(II) ions and μ3-HPyIDC2− anions, whereas the metal centers of complex 2 are bridged by μ2-HPyIDC2− ligands. Complex 3 possesses a two-dimensional grid-like network consisting of four-connected Pb(II) ions and two-connected μ2-H2PyIDC− anions. Complex 4 has a two-dimensional honeycomb-like network structure, which is composed of μ3-HPyIDC2− ligands and Mg(II) ions. In complex 5, the extended Mg(II)-carboxylate 1D zigzag chains are connected by pyridyl nitrogen atoms of HPyIDC2− ligands to form a three-dimensional open framework. The thermal stabilities of complexes 1, 3–5 and solid-state luminescent properties of complexes 1–5 have been investigated.Graphical abstractThe structural variation of five main group complexes is primary attributed to the coordination geometries of the metal ions, the various coordination modes of the H3PyIDC ligands and the anions. Moreover, the photoluminescent properties and thermal behaviors of selected complexes were investigated.Highlights► Five main group metal coordination polymers based on H3PyIDC were obtained. ► These complexes exhibited various networks from 1D chain to 3D framework. ► The H3PyIDC ligand displays various coordination modes. ► These complexes exhibit strong emissions, varying from violet-blue to green fluorescence.
Co-reporter:Zhi-Li Fang, Sheng-Run Zheng, Jun Fan, Wei-Guang Zhang
Inorganic Chemistry Communications 2012 20() pp: 122-125
Publication Date(Web):
DOI:10.1016/j.inoche.2012.02.032
Co-reporter:Sheng-Run Zheng, Song-Liang Cai, Mei Pan, Jun Fan, Tian-Tian Xiao and Wei-Guang Zhang
CrystEngComm 2011 vol. 13(Issue 3) pp:883-888
Publication Date(Web):12 Oct 2010
DOI:10.1039/C0CE00369G
Reaction of Cd(II), Fe(II), and Cu(II) with a new ligand 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid (H4hmIDC) and 4,4′-bipyridine (bpy) affords three coordination polymers of {[Cd(H2hmIDC)(bpy)]·0.5bpy·H2O}n (1), [Fe2(HhmIDC)2]n (2), and {[Cu2(ITC)(bpy)(H2O)3]·2.5H2O}n (3) (ITC = imidazole-2,4,5-tricarboxylic acid), respectively. Complex 1 and complex 3 are (4,4) nets in topological view and display in different packing mode, while hydroxymethyl group in complex 3 is oxidized to carboxylic groupin situ. Complex 2 is a rare example of a cdl-e network containing both tetrahedral and square nodes. The hydroxymethyl groups act as a precursor and undergo different reactions directed by metal ions.
Co-reporter:Song-Liang Cai, Sheng-Run Zheng, Jing-Bo Tan, Mei Pan, Jun Fan and Wei-Guang Zhang
CrystEngComm 2011 vol. 13(Issue 21) pp:6345-6348
Publication Date(Web):19 Sep 2011
DOI:10.1039/C1CE05535F
An unprecedented supramolecular network formed by [Ag(4,4′-bipyridine)]n chains and [Ag(NO3)4]3− anions via Ag⋯O interaction shows four types of channels filled by [Ag(4,4′-bipyridine)]n chains, [Ag(benzimidazole)]n chains and water molecules, representing the first example of cocrystallization of two 1D infinite coordination polymer chains.
Co-reporter:Jixia Mou, Weiguang Zhang, Jun Fan, Hong Deng, Wei Chen
Journal of Alloys and Compounds 2011 Volume 509(Issue 3) pp:961-965
Publication Date(Web):21 January 2011
DOI:10.1016/j.jallcom.2010.09.148
In this paper we reported a successful synthesis of ZnO nanobullets/nanoflakes by a simple hydro/solvothermal method employing a mixture of water/ethylene glycol as the solvent, and zinc acetate as the zinc source. The final products were characterized by powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Raman scattering and photofluorescence spectra of the products were also investigated. ZnO with both nanobullets and nanoflakes nanostructures had been comparably studied as active photoanodes in dye-sensitized solar cell (DSSC) system, and the overall light-to-energy conversion efficiency of 1.93% has been achieved for nanobullets based DSSC, while that for ZnO nanoflakes based DSSC has been raised up to 3.64%.Research highlights▶Although there are many available methods to fabricate ZnO nanostructures, we report here a simple and generalized method to prepare ZnO nanocrystallites from zinc acetates by tuning the volume ratio between water and ethylene glycol. In comparison, this synthetic method is of relatively low cost and is able to readily scaled-up for industrial production. In particular, the ZnO nanostructures were used as active photoanodes after incorporation in sandwich-type dye-sensitized solar cells (DSSCs). The overall solar-to-electric energy conversion efficiencies obtained under air mass (AM) 1.5 conditions, were 1.93% using ZnO nanobullets, while the efficiency was raised up to 3.64% using ZnO nanoflakes.
Co-reporter:Xia Yin, Jun Fan, Zhi Hong Wang, Sheng Run Zheng, Jing Bo Tan, Wei Guang Zhang
Journal of Solid State Chemistry 2011 Volume 184(Issue 7) pp:1850-1857
Publication Date(Web):July 2011
DOI:10.1016/j.jssc.2011.05.018
Four new luminescent complexes, namely, [Eu(aba)2(NO3)(C2H5OH)2] (1), [Eu(aba)3(H2O)2]·0.5 (4, 4′-bpy)·2H2O (2), [Eu2(aba)4(2, 2′-bpy)2(NO3)2]·4H2O (3) and [Tb2(aba)4(phen)2(NO3)2]·2C2H5OH (4) were obtained by treating Ln(NO3)3·6H2O and 4-acetamidobenzoic acid (Haba) with different coligands (4, 4′-bpy=4, 4′–bipyridine, 2, 2′-bpy=2, 2′-bipyridine, and phen=1, 10-phenanthroline). They exhibit 1D chains (1–2) and dimeric structures (3–4), respectively. This structural variation is mainly attributed to the change of coligands and various coordination modes of aba molecules. Moreover, the coordination units are further connected via hydrogen bonds to form 2D even 3D supramolecular networks. These complexes show characteristic emissions in the visible region at room temperature. In addition, thermal behaviors of four complexes have been investigated under air atmosphere. The relationship between the structures and physical properties has been discussed.Graphical abstractStructure variation of four complexes is attributed to the change of coligands and various coordination modes of aba molecules. Moreover, they show characteristic emissions in the visible region. Highlights► Auxiliary ligands have played the crucial roles on the structures of the resulting complexes. ► Isolated structure units are further assembled via H-bonds to form supramolecular networks. ► These solid-state complexes exhibit strong, characteristic emissions in the visible region.
Co-reporter:Sheng-Run Zheng, Song-Liang Cai, Qing-Yuan Yang, Tian-Tian Xiao, Jun Fan, Wei-Guang Zhang
Inorganic Chemistry Communications 2011 Volume 14(Issue 6) pp:826-830
Publication Date(Web):June 2011
DOI:10.1016/j.inoche.2011.02.021
Two new porous lanthanide-organic frameworks, {[Ln2(HIDC)3(H2O)2]·7H2O}n [Ln = Tb(1) and Eu(2), H3IDC = imidazole-4,5-dicarboxylic acid], were obtained under hydrothermal conditions. Both of them possess 3D frameworks containing 1D rectangle channels along a-axis. Topological analyses of two complexes reveal that they exhibit unusual 4-nodal (3,4)-connected network. Furthermore, their solid-state luminescent behaviors have been investigated at room temperature.Two 3D porous lanthanide-organic frameworks containing 1D rectangle channels along a direction feature unusual 4-nodal (3,4)-connected network topology as well as show strong fluorescent emission.Research Highlights► Two 3D porous frameworks constructed by H3IDC ligand and lanthanides ions. ► Frameworks containing 1D rectangle channels. ► Frameworks with novel four-nodal (3,4)-connected network topology.
Co-reporter:Sheng-Run Zheng, Song-Liang Cai, Jun Fan, Tian-tian Xiao, Wei-Guang Zhang
Inorganic Chemistry Communications 2011 Volume 14(Issue 6) pp:818-821
Publication Date(Web):June 2011
DOI:10.1016/j.inoche.2011.02.017
Two new coordination polymers, {[Mn3(BIC)3(H2O)4]∙C2H5OH∙H2O}n (1) and {[Mn3(BIC)3(H2O)4]∙C3H6O∙H2O}n (2, C3H6O = acetone), were obtained under hydrothermal conditions. Both of them are 2D networks containing bowl-shaped voids, which are occupied by EtOH and Me2CO molecules, respectively. Furthermore, the single 2D layer is chiral, which is assembled by the bis(chelating) bridging ligands and two kinds of Mn(II) coordination units.Two 2D Mn(II) coordination polymers containing bowl-shaped voids and containing homochiral layer assembled from the bis(chelating) bridging ligand and two kinds of Mn(II) units.Research Highlights► They are first 2D coordination polymers based on bisdidentate BIC2− ligands. ► Coordination polymers containing neutral homochiral honeycomb layers. ► Coordination polymers containing bowl-shaped neutral space.
Co-reporter:Song-Liang Cai, Sheng-Run Zheng, Jun Fan, Tian-Tian Xiao, Jing-Bo Tan, Wei-Guang Zhang
Inorganic Chemistry Communications 2011 Volume 14(Issue 6) pp:937-939
Publication Date(Web):June 2011
DOI:10.1016/j.inoche.2011.03.036
Co-reporter:Jun Fan, Tian-tian Xiao, Sheng-Run Zheng, Song-Liang Cai, Wei-Guang Zhang
Inorganic Chemistry Communications 2011 Volume 14(Issue 7) pp:1156-1160
Publication Date(Web):July 2011
DOI:10.1016/j.inoche.2011.04.012
Two new coordination frameworks, namely, [Zn2(aip)(Haip)2(H2O)2]⋅2H2O (1) and [Cu2(aip) (H2O)(μ3-OH)2] (2),were synthesized from the corresponding metal salts with 5-aminophthalic acid (H2aip) under hydrothermal conditions. They possess interesting 3D architectures constructed from the rod-shaped secondary building blocks with 5-nodal (3, 4, 5, 6)-connected and (3, 5, 6)-connected network topologies, respectively. Moreover, luminescent behaviors of two complexes have been investigated at room temperature and they show the intense blue emissions.Two new 3D coordination polymers possess 3D architectures constructed from the rod-shaped SBUs with 5-nodal network topologies as well as show the intense blue emission at room temperature.Research Highlights► Two complexes 1–2 are assembled by 1D rod-shaped secondary building blocks. ► They show 3D metal-organic frameworks with 5-nodal network topologies. ► They have different topologies, due to multiple coordination modes of aip anions.
Co-reporter:Sheng-Run Zheng, Song-Liang Cai, Jun Fan, Tian-Tian Xiao, Wei-Guang Zhang
Inorganic Chemistry Communications 2011 Volume 14(Issue 7) pp:1097-1101
Publication Date(Web):July 2011
DOI:10.1016/j.inoche.2011.03.065
Three new complexes, [Cd(H2hmIDC)(bpy)]n (1), {[Co4(HIDC)4(bpy)4]·14H2O}n (2) and {[Co5(IDC)2(HIDC)2(phen)4(H2O)2]·12H2O}n (3) (H4hmIDC = 2-(hydroxymethyl)-1 H-imidazole-4,5-dicarboxylic acid, H3IDC = imidazole-4,5-dicarboxylic acid, bpy = 2,2’-bipyridyl, phen = 1,10-phenanthroline), were obtained under hydrothermal conditions by using H4hmIDC as initial reactant. Complex 1 is a zigzag chain containing angular [Cd(phen)]2+ node and H2hmIDC2- linker, compound 2 is a discrete Co4 square, while 3 is a 1D chain based on Co4 square motifs similar to that in complex 2. In complex 1, the hydroxymethyl group of the H4hmIDC molecule retains integrated and acts as effective hydrogen bonding interaction site, while in complexes 2 and 3, all the hydroxymethyl groups are lost in situ. The hydroxymethyl groups undergo different reactions directed by metal ions.The hydroxymethyl group of the imidazole-based dicarboxylate ligand undergo different reactions directed by metal ions.Research Highlights►The imidazole-based dicarboxylate ligand containing hydroxymethyl group. ►The ligand undergoes different reactions directed by metal ions. ►The ligand undergoes in situ C–C cleavage reaction. ►A 1D coordination chain based on Co4 squares and Co(II) linker.
Co-reporter:Jun Fan, Zhi-Hong Wang, Ming Yang, Xia Yin, Wei-Guang Zhang, Zhuo-Fen Huang and Rong-Hua Zeng
CrystEngComm 2010 vol. 12(Issue 1) pp:216-225
Publication Date(Web):03 Sep 2009
DOI:10.1039/B910219A
Hydrothermal reactions of Ln(NO3)3 and (8-quinolyloxy)acetic acid (HQOA) with auxiliary ligands resulted in a series of new one-, two- and three-dimensional (1D, 2D and 3D) coordination polymers, namely, [Ln(QOA)2 (H2O)2]·NO3·H2O [Ln = Eu (1), Gd (2)], [Ln2(QOA)4(ox)(H2O)]·3H2O [Ln = Pr (3), Er (4)], [Ln2(QOA)4(BDC) (H2O)]·4H2O [Ln = Sm (5)] and [Ln(QOA)(BDC)] [Ln = Sm (6), Eu (7)] [QOA = (8–quinolyloxy)acetate; ox = oxalate; BDC = 1, 4–benzenedicarboxylate], respectively. Compounds 1–2 possess 1D zigzag chains bridged by QOA anions and 3–4 contain 1D folded chains alternately bridged by oxalates and QOA anions. Complex 5 is an ordered (2,4)–connected 2D sheet-like structure. In compounds 6–7, four BDC anions bridge two adjacent metal atoms to form dinuclear lanthanide building blocks and these dinuclear blocks are further connected together to form an 8-connected 3D network. The progressive variation from 1D zigzag chains (1–2) to 1D folded chains (3–4) to a 2D layer network (5) and to 3D frameworks (6–7) is mainly attributed to the change of bridging ligands as well as the different coordination modes of organic carboxylic ligands. Moreover, the thermal stabilities and photoluminescent properties of these compounds show a remarkable difference due to the progressive variation of crystal structures.
Co-reporter:Chun Lin;Wenjun Luo;Sheng Zhang;Zhenbin Zhang;Weiguang Zhang;Shengrun Zheng;Jun Fan;Weishan Li;Qing Qin;Ziyuan Guo
Journal of Separation Science 2010 Volume 33( Issue 11) pp:1558-1562
Publication Date(Web):
DOI:10.1002/jssc.200900826
Abstract
Two types of chiral stationary phases for HPLC based on π-acidic or π-basic perphenylcarbamoylated β-CDs were synthesized. The relative structural features of the two effective chiral selectors are discussed and compared in both normal-phase and RP modes. In addition, the nature and concentration of alcoholic modifiers were varied for optimal separation in normal phase and the structural variation of the analytes was also examined. The results showed that hydrogen bonding, steric effect and π-acidic–π-basic interaction contributed greatly to enantioseparation. Upon comparison, some of the differences in the separation behavior of the two types of chiral stationary phases might be due to the π-acidic or π-basic phenylcarbamate groups.
Co-reporter:Qing Qin;Sheng Zhang;Zhen-Bin Zhang;Ya-Jin Xiong;Zi-Yuan Guo;Jun Fan;Sheng Run-Zheng;David Finlow;Yong Yin
Journal of Separation Science 2010 Volume 33( Issue 17-18) pp:2582-2589
Publication Date(Web):
DOI:10.1002/jssc.200900831
Abstract
In this study, the CD derivative, mono (6A-azido-6A-deoxy)-per(p-chlorophenylcarbamonylated) β-CD was chemically immobilized onto the surface of an amino-functionalized silica gel with different pore (100, 300, and 500Å) and particle (3, 5, and 10 μm) sizes to obtain novel chiral stationary phases. The impact of pore and particle size on the amount of immobilized Ph-β-CD, column performance, and enantioselectivity was investigated by evaluating the separation of a variety of racemates in both the normal- and the reversed-phase modes. Experimental results revealed that the retention factor and resolution of racemates generally decreased with increasing pore size; the column prepared with the smallest (3 μm) silica gel particle size gave the best column performance and enantioselectivity in both the normal- and the reversed-phase modes.
Co-reporter:Jun Wang, Jun Fan, LiangYu Guo, Xia Yin, ZhiHong Wang, WeiGuang Zhang
Journal of Solid State Chemistry 2010 Volume 183(Issue 3) pp:575-583
Publication Date(Web):March 2010
DOI:10.1016/j.jssc.2009.12.027
Five new lanthanide supramolecular complexes, namely, [Sm(oqa)2(H2O)4]2 (ClO4)2·(bpy)2 (1), [Ln(oqa)3]·2H2O [Ln=Sm(2), Gd(3)] and [Ln(oqa)2(NO3)(H2O)] [Ln=Pr(4), Eu(5)] (oqa=4-oxo-1(4H)-quinolineacetate, bpy=4,4′-bipyridine), have been synthesized under hydrothermal conditions. These complexes exhibit three typical structure features. Complex 1 possesses a dimeric structure, which is further connected together through hydrogen bonds and π–π attractions, forming a 3D supramolecular framework. Compounds 2–3 are isomorphous and contain 1D ring-like chains, which are further interconnected by the oqa ligands into 2D sheet-like structures. 4 and 5 exhibit eight-connected 3D network of 424·64-bcu topology. The various coordination modes of carboxylate ligands and the selection of the counterions have clearly affected the topological structures. Furthermore, the solid-state luminescent properties of complexes 1, 2 and 5 were investigated at room temperature and they show intense, characteristic emissions in the visible region.The hydrothermal reactions of the oqa molecules with varied lanthanide ions resulted in the formation of five new complexes, which exhibit three typical structure features.
Co-reporter:Jun Wang, Jun Fan, Liang-Yu Guo, Xia Yin, Zhi-Hong Wang, Wei-Guang Zhang
Inorganic Chemistry Communications 2010 Volume 13(Issue 2) pp:322-325
Publication Date(Web):February 2010
DOI:10.1016/j.inoche.2009.12.015
Co-reporter:Jun Fan, Zhi-Hong Wang, Zhuo-Fen Huang, Xia Yin, Wei-Guang Zhang
Inorganic Chemistry Communications 2010 Volume 13(Issue 5) pp:659-662
Publication Date(Web):May 2010
DOI:10.1016/j.inoche.2010.03.013
Two new lanthanide supramolecular complexes, [Tb(qoa)2(H2O)2]⋅NO3 ⋅ H2O (1) and [Er(qoa)3] ⋅ 2H2O (2) [qoa = (8-quinolinyloxy)acetate] were obtained by treating the corresponding nitrates and (8-quinolinyloxy)acetic acid (Hqoa) under hydrothermal conditions. Complex 1 possesses a 1D zigzag chain bridged by the qoa anions, which is further connected to form a 3D supramolecular framework via hydrogen bonds and π–π attractions. Compound 2 is a mononuclear structure and the coordination units are further assembled to a 1D helical chain parallel to the b-axis via hydrogen bonds. Obviously, various coordination modes of the qoa anions and the intermolecular attractions have effect on the formations of two complexes. The solid-state luminescent behavior of 1 has been investigated at room temperature.Two new lanthanide complexes exhibit different structure features, namely, a 1D zigzag chain and a helical chain. Various coordination modes of the ligands have influenced the formation of these complexes.
Co-reporter:Miao Li Luo;Wei Guang Zhang;Sheng Zhang;Jun Fan;Wen Cui Su;Xia Yin
Chirality 2010 Volume 22( Issue 4) pp:411-415
Publication Date(Web):
DOI:10.1002/chir.20756
Abstract
A novel chiral sensor based on the self-assembled monolayer of (6A-ω-mercaptoethylureado-6A-deoxy)heptakis(2,3-di-o-phenylcarbamoyl)-6B, 6C, 6D, 6E, 6F, 6G- hexa-o-phenylcarbamoyl-β-cyclodextrin (Ph-β-CD-SH) on a quartz crystal transducer for chiral recognition was set up. (R,S)-(±)-(3-Methoxyphenyl)ethylamine were recognized by this QCM chiral sensor with a QCM chiral discrimination factor of 1.33. Furthermore, UV spectroscopy was used to investigate the mechanism of host-guest interactions between (6A-azido-6A-deoxy)heptakis(2,3-di-o-phenylcarbamoyl)-6B, 6C, 6D, 6E, 6F, 6G-hexa-o-phenylcarbamoyl-β-cyclodextrin (Ph-β-CD) and (R,S)-(±)-(3-methoxyphenyl) ethylamine. The UV discrimination factor was determined to be 0.066. Chirality, 2010. © 2009 Wiley-Liss, Inc.
Co-reporter:Jun Wang;Jun Fan;Zhi-hong Wang
Journal of Chemical Crystallography 2009 Volume 39( Issue 8) pp:585-588
Publication Date(Web):2009 August
DOI:10.1007/s10870-009-9530-3
Co-reporter:Wen Cui Su, Wei Guang Zhang, Sheng Zhang, Jun Fan, Xia Yin, Miao Li Luo, Siu Choon Ng
Biosensors and Bioelectronics 2009 Volume 25(Issue 2) pp:488-492
Publication Date(Web):15 October 2009
DOI:10.1016/j.bios.2009.06.040
A novel and effective method has been developed for chiral discrimination using a quartz crystal microbalance (QCM) biosensor with self-assembled bovine serum albumin (BSA) or human serum albumin (HSA). The successfully constructed QCM chiral biosensors exhibited rapid and real-time enantioselective recognition. The QCM chiral discrimination factor (αQCM) can be calculated through resonance frequency shifts in response to five pairs of enantiomers. Moreover, the interactions between these ten enantiomers and two serum albumins (SA) were investigated in detail by means of ultraviolet–visible (UV–vis) and fluorescence (FL) spectra. The results indicated that the discrimination ability were quite different between BSA and HSA. R,S-1-(3-Methoxyphenyl)ethylamine (R,S-3-MPEA) and R,S-1-(4-methoxyphenyl)ethylamine (R,S-4-MPEA) can be easily differentiated by the BSA sensor, while the selectivity of the HSA sensor for R,S-tetrahydronaphthylamine (R,S-TNA), R,S-2-octanol (R,S-2-OT) and R,S-methyl lactate (R,S-MEL) was higher than that of the BSA sensor. The UV and FL spectra indicated the formation of a complex between SA and enantiomers and strong fluorescence quenching through static quenching mechanism. The in-depth study demonstrated that the calculated UV/FL discrimination factors (αUV and αFL) were consistent with the QCM experimental results (αQCM).
Co-reporter:Xia Yin;Weiguang Zhang;Qijiao Zhang;Jun Fan;Chian Sing Lai;Edward R. T. Tiekink
Applied Organometallic Chemistry 2004 Volume 18(Issue 3) pp:
Publication Date(Web):10 FEB 2004
DOI:10.1002/aoc.528
The centrosymmetric structure of {Cd[S2CN(CH2Ph)2]2}2 features both bridging and chelating dithiocarbamate ligands so that a square pyramidal S5 coordination geometry results. Copyright © 2004 John Wiley & Sons, Ltd.
Co-reporter:Jun Fan;Min-Yu Tan;Yu Tang;Wei-Sheng Liu;Ning Tang;Kai-Bei Yu
Chinese Journal of Chemistry 2004 Volume 22(Issue 6) pp:
Publication Date(Web):26 AUG 2010
DOI:10.1002/cjoc.20040220603
The La(III) complex with a new amide-type tripodal ligand,2,2′.2″-nitrilotris{[(2′-benzylaminofomyl)-phenoxylethyl)amine (L), was synthesized and characterized by X-ray crystallographic analysis. Crystal data: C48H55.50LaN7O18.75, Mr=1169.40, monoclinic. space group, P21/n, a= 1.0644(3) nm. b=2.3889(5) nm, c= 2.1917(5) nm, β=90.65°, V=5.573(2) nm3, Z=1, Dc=1.394 g°cm−3, R1=0.0487, wR [1>2s̀(I)]=0.1266. The results reveal that each La(III) ion binds to 9 oxygen atoms, three of which belong to carbonyl groups from three tripodal ligands and six to three bidentate nitrate groups and a two-dimensional sheet of 4.82 networks is assembled by metal-ligand coordination interaction. L, a heptadentate compound, merely acts as a tridentate bridging spacer due to its steric hindrance and links the La(III) ions as three-connected nodes.
Co-reporter:Xia Yin;Weiguang Zhang;Jun Fan;Feng Xian Wei;Chian Sing Lai;Edward R. T. Tiekink
Applied Organometallic Chemistry 2003 Volume 17(Issue 11) pp:
Publication Date(Web):9 OCT 2003
DOI:10.1002/aoc.538
The centrosymmetric structure of {Zn[S2CN(CH2Ph)2]2}2(4,4′-bipy) features chelating dithiocarbamate ligands so that a trigonal bipyramidal NS4 coordination geometry for zinc results. Copyright © 2003 John Wiley & Sons, Ltd.
Co-reporter:Wei-Guang Zhang;Yun Zhong;Min-Yu Tan;Wei-Sheng Liu;Cheng-Yong Su
Chinese Journal of Chemistry 2002 Volume 20(Issue 5) pp:
Publication Date(Web):26 AUG 2010
DOI:10.1002/cjoc.20020200503
The first crystal structural report of a AgDTC complex (DTC = dialkyldithiocarbamate, R = n-butyl) presented in this paper shows that it is a hexanuclear species. The structural arrangement for the DDP (dialkyldithiophosphate) ligands is different from that of Cu6(DDP)6, but is the same as that of Ag6-[SSP(O-i-Pr)2]6.
Co-reporter:Song-Liang Cai, Yue-Biao Zhang, Andrew B. Pun, Bo He, Jinhui Yang, Francesca M. Toma, Ian D. Sharp, Omar M. Yaghi, Jun Fan, Sheng-Run Zheng, Wei-Guang Zhang and Yi Liu
Chemical Science (2010-Present) 2014 - vol. 5(Issue 12) pp:NaN4700-4700
Publication Date(Web):2014/09/16
DOI:10.1039/C4SC02593H
Despite the high charge-carrier mobility in covalent organic frameworks (COFs), the low intrinsic conductivity and poor solution processability still impose a great challenge for their applications in flexible electronics. We report the growth of oriented thin films of a tetrathiafulvalene-based COF (TTF-COF) and its tunable doping. The porous structure of the crystalline TTF-COF thin film allows the diffusion of dopants such as I2 and tetracyanoquinodimethane (TCNQ) for redox reactions, while the closely packed 2D grid sheets facilitate the cross-layer delocalization of thus-formed TTF radical cations to generate more conductive mixed-valence TTF species, as is verified by UV-vis-NIR and electron paramagnetic resonance spectra. Conductivity as high as 0.28 S m−1 is observed for the doped COF thin films, which is three orders of magnitude higher than that of the pristine film and is among the highest for COF materials.
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