Metal-Controlled Assembly Tuning Coordination Polymers with Flexible 2-(1H-imidazole-1-yl)acetic Acid (Hima)

2006 ◽  
Vol 59 (9) ◽  
pp. 647 ◽  
Author(s):  
Yong-Tao Wang ◽  
Gui-Mei Tang ◽  
Da-Wei Qin

Three new inorganic–organic coordination polymers based on a versatile linking unit 2-(1H-imidazole-1-yl)acetate (Hima) and divalent Mn(ii), Ni(ii), and Cu(ii) ions, exhibiting two kinds of two dimensionalities with different topological structures, have been prepared in water medium and structurally characterized by single-crystal X-ray diffraction analysis. Reaction of MnCl2·4H2O and Ni(NO3)2·6H2O with Hima yielded neutral two-dimensional (2D) coordination polymers [M(ima)2]n, M = Mn(ii) 1, and Ni(ii) 2 with isostructural 2D coordination polymers possessing (3,6) topology structures, which further stack into three-dimensional (3D) supramolecular networks through C–H···O weak interactions. However, when Cu(NO3)2·4H2O was used, a neutral 2D coordination polymer [Cu(ima)2]n 3 consisting of rhombus units was generated, which showed a 3D supramolecular network through C–H···O weak interactions. Among these polymers, the building block ima anion exhibits different coordination modes. These results indicate that the versatile nature of this flexible ligand, together with the coordination preferences of the metal ions, plays a critical role in construction of these novel coordination polymers. Spectral and thermal properties of these new materials have also been investigated.

2007 ◽  
Vol 62 (2) ◽  
pp. 195-199 ◽  
Author(s):  
Dongmei Shi ◽  
Haijun Pang ◽  
Fanxia Meng ◽  
Yu Sun ◽  
Kun Liu ◽  
...  

A new organic/inorganic salt formed by mixed-valence dibenzotetrathiafulvalene (DBTTF) radical cations and the spherical Keggin-type polyoxometalate anions [H3BW12O40]2− was obtained by electrochemical oxidation of the donor in an acetonitrile and a 1,2-dichloroethane solution containing the polyanion. The compound has been characterized by X-ray diffraction, elemental analysis, EPR, IR and Raman spectroscopy. X-Ray diffraction experiments have revealed that the compound consists of heteropolyanions, water molecules and DBTTF radical cations. The organic radicals form trimers and dimers via π-π stacking; moreover, the polyoxoanions and the organic donors are also held together by hydrogen bonding interactions. In their packing arrangement, a three-dimensional supramolecular network with one-dimensional channels along the b axis is established with uncoordinated water molecules residing in the channels.


2019 ◽  
Vol 74 (3) ◽  
pp. 261-265 ◽  
Author(s):  
Gao-Feng Wang ◽  
Shu-Wen Sun ◽  
Wei-Bing Wang ◽  
Hong Sun ◽  
Shao-Fei Song

AbstractTwo coordination polymers, {[Co(bipmo)(tbip)]·3H2O}n (1) and {[Cd(bipmo)(tbip)]·3H2O}n (2) (bipmo=bis(4-(1H-imidazol-1-yl)phenyl)methanone, H2tbip=5-tert-butylisophthalic acid), were synthesized by solvothermal methods and structurally characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray diffraction. The results from single-crystal X-ray diffraction data indicate that the solid state structures of 1 and 2 consist of metal-aromatic carboxylate layers, which are pillared by weak interactions to generate a three-dimensional network. The topological structures of 1 and 2 are uninodal nets based on 3-connected nodes with the Schläfli symbol of {63}.


2019 ◽  
Vol 75 (2) ◽  
pp. 120-127 ◽  
Author(s):  
Rafika Bouchene ◽  
Sofiane Bouacida

Two new coordination polymers, namely poly[[(3-aminopyrazin-4-ium-2-carboxylate-κ2 N 1,O)di-μ-chlorido-cadmium(II)] monohydrate], {[CdCl2(C5H5N3O2)]·H2O} n , (1), and poly[2-amino-3-carboxypyrazin-1-ium [(3-aminopyrazine-2-carboxylato-κ2 N 1,O)di-μ-chlorido-cadmium(II)] monohydrate], {(C5H6N3O2)[Cd(C5H4N3O2)Cl2]·H2O} n , (2), have been synthesized from the reaction of cadmium(II) chloride and 3-aminopyrazine-2-carboxylic acid (Hapca) under mild conditions in acidic media. The two coordination polymers have been characterized by single-crystal X-ray diffraction and show chloride-bridged zigzag chains with octahedrally coordinated metal ions, where Hapca acts as a bidentate ligand via the π-conjugated N atom and a carboxylate O atom. The chains are further interconnected via noncovalent interactions into three-dimensional supramolecular networks. The dominant H...O and H...Cl interactions for both compounds were quantified using Hirshfeld surface analysis. The thermal stability and topological analysis of the two-dimensional networks of (1) and (2) are also discussed.


Crystals ◽  
2018 ◽  
Vol 8 (10) ◽  
pp. 372
Author(s):  
Mei-An Zhu ◽  
Shuai-Shuai Han ◽  
Feng Deng ◽  
Jia-Le Li ◽  
Shui-Sheng Chen

The coordination polymer, namely, [Cd(H2L)(nobda)]n (1) was prepared by the reaction of Cd(NO3)2·4H2O with 4-amino-1,2-benzenedicarboxylic acid (H2nobda) and 1,4-di(1H-imidazol-4-yl)benzene (H2L), and characterized by single-crystal X-ray diffraction, elemental analysis, infrared (IR) spectroscopy, thermogravimetric analysis, and powder X-ray diffraction (PXRD). The carboxylic acid of H2nobda ligands was completely deprotonated to be nobda2− anions, which act as tridentate ligand to connect the Cd2+ to form two-dimensional (2D) network, while the neutral H2L ligands serve as a linear didentate bridge to connect two adjacent Cd2+ ions upper and down the 2D layer. The adjacent 2D layers were further linked into the three-dimensional (3D) supramolecular polymer by the weak interactions such as hydrogen bonds and π−π stacking interactions. The ultraviolet-visible (UV-vis) absorption spectra and luminescent properties in the solid state at room temperature have been investigated.


Crystals ◽  
2018 ◽  
Vol 8 (11) ◽  
pp. 424 ◽  
Author(s):  
Jia-Le Li ◽  
Wei-Dong Li ◽  
Zi-Wei He ◽  
Shuai-Shuai Han ◽  
Shui-Sheng Chen

A new compound, namely, [Zn(L)2]n (1) was obtained by the reaction of 2-methyl-4-(4H-1,2,4-triazol-4-yl) benzoic acid (HL) with ZnSO4·7H2O, and the compound was characterized by single-crystal X-ray diffraction, infrared spectroscopy, elemental analysis, powder X-ray diffraction (PXRD), and thermogravimetric analysis. The linear HL ligands were deprotonated to be L− anions and act as two-connectors to link Zn2+ to form a two-dimensional (2D) lay structure with (4, 4) topology. The large vacancy of 2D framework allows another layer structure to interpenetrate, resulting in the formation of 2D + 2D → 2D parallel interpenetration in 1. The weak interactions, such as hydrogen bonding and π–π stacking interactions, connect the adjacent 2D layers into a three-dimensional (3D) coordination polymer. The solid-state UV-visible spectroscopy and luminescent property have also been studied.


2020 ◽  
Vol 76 (11) ◽  
pp. 1024-1033
Author(s):  
Fang-Hua Zhao ◽  
Shi-Yao Li ◽  
Wen-Yu Guo ◽  
Zi-Hao Zhao ◽  
Xiao-Wen Guo ◽  
...  

Two new CdII MOFs, namely, two-dimensional (2D) poly[[[μ2-1,4-bis(1H-benzimidazol-1-yl)butane](μ2-heptanedioato)cadmium(II)] tetrahydrate], {[Cd(C7H10O4)(C18H18N4)]·4H2O} n or {[Cd(Pim)(bbimb)]·4H2O} n (1), and 2D poly[diaqua[μ2-1,4-bis(1H-benzimidazol-1-yl)butane](μ4-decanedioato)(μ2-decanedioato)dicadmium(II)], [Cd2(C10H16O4)2(C18H18N4)(H2O)2] n or [Cd(Seb)(bbimb)0.5(H2O)] n (2), have been synthesized hydrothermally based on the 1,4-bis(1H-benzimidazol-1-yl)butane (bbimb) and pimelate (Pim2−, heptanedioate) or sebacate (Seb2−, decanedioate) ligands. Both MOFs were structurally characterized by single-crystal X-ray diffraction. In 1, the CdII centres are connected by bbimb and Pim2− ligands to generate a 2D sql layer structure with an octameric (H2O)8 water cluster. The 2D layers are further connected by O—H...O hydrogen bonds, resulting in a three-dimensional (3D) supramolecular structure. In 2, the CdII centres are coordinated by Seb2− ligands to form binuclear Cd2 units which are linked by bbimb and Seb2− ligands into a 2D hxl layer. The 2D layers are further connected by O—H...O hydrogen bonds, leading to an 8-connected 3D hex supramolecular network. IR and UV–Vis spectroscopy, thermogravimetric analysis and solid-state photoluminescence analysis were carried out on both MOFs. Luminescence sensing experiments reveal that both MOFs have good selective sensing towards Fe3+ in aqueous solution.


2019 ◽  
Vol 75 (8) ◽  
pp. 1073-1083 ◽  
Author(s):  
Feng Su ◽  
Cheng-Yong Zhou ◽  
Lin-Tao Wu ◽  
Xi Wu ◽  
Jing Su ◽  
...  

Two CoII-based coordination polymers, namely poly[(μ4-biphenyl-2,2′,5,5′-tetracarboxylato){μ2-1,3-bis[(1H-imidazol-1-yl)methyl]benzene}dicobalt(II)], [Co2(C16H6O8)(C14H14N4)2] n or [Co2(o,m-bpta)(1,3-bimb)2] n (I), and poly[[aqua(μ4-biphenyl-2,2′,5,5′-tetracarboxylato){1,4-bis[(1H-imidazol-1-yl)methyl]benzene}dicobalt(II)] dihydrate], {[Co2(C16H6O8)(C14H14N4)2(H2O)2]·4H2O} n or {[Co2(o,m-bpta)(1,4-bimb)2(H2O)2]·4H2O} n (II), were synthesized from a mixture of biphenyl-2,2′,5,5′-tetracarboxylic acid, i.e. [H4(o,m-bpta)], CoCl2·6H2O and N-donor ligands under solvothermal conditions. The complexes were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction and powder X-ray diffraction analysis. The bridging (o,m-bpta)4− ligands combine with CoII ions in different μ4-coordination modes, leading to the formation of one-dimensional chains. The central CoII atoms display tetrahedral [CoN2O2] and octahedral [CoN2O4] geometries in I and II, respectively. The bis[(1H-imidazol-1-yl)methyl]benzene (bimb) ligands adopt trans or cis conformations to connect CoII ions, thus forming two three-dimensional (3D) networks. Complex I shows a (2,4)-connected 3D network with left- and right-handed helical chains constructed by (o,m-bpta)4− ligands. Complex II is a (4,4)-connected 3D novel network with ribbon-like chains formed by (o,m-bpta)4− linkers. Magnetic studies indicate an orbital contribution to the magnetic moment of I and II due to the longer Co...Co distances. An attempt has been made to fit the χM T results to the magnetic formulae for mononuclear CoII complexes, the fitting indicating the presence of weak antiferromagnetic interactions between the CoII ions.


2015 ◽  
Vol 68 (1) ◽  
pp. 121 ◽  
Author(s):  
Wenlong Liu ◽  
Xueying Wang ◽  
Mengqiang Wu ◽  
Bing Wang

Two new coordination polymers, namely, {[Cd3(bpt)2(bimb)2]·2(H2O)}n (1) and [Zn3(bpt)2(bimb)2]n (2) (bpt = biphenyl-3,4′,5-tricarboxylate, bimb = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene), have been obtained under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analysis and further characterised by elemental analysis and infrared spectroscopy. Complex 1 exhibits a trinodal (4,4,4)-connected topology with Schläfli symbol of (4.62.83)4.(64.82). Complex 2 is also a three-dimensional structure and displays a (3,4,6)-connected topology with Schläfli symbol of (4.62)2.(42.66.85.102).(64.82). It is shown that the asymmetrically tricarboxylate can bear diverse structures regulated by metal ions. The photoluminescence behaviours of compounds 1 and 2 were also discussed.


2018 ◽  
Vol 74 (8) ◽  
pp. 951-960 ◽  
Author(s):  
Chong Zhang ◽  
Kou-Lin Zhang

The bromo-substituted aromatic dicarboxylic acid 5-amino-2,4,6-tribromoisophthalic acid (H2ATBIP) was used to assemble with CdII ions in the presence of the N-donor flexible bipyridyl ligands 3,3′-(diazene-1,2-diyl)dipyridine (mzpy) and 1,3-bis(pyridin-3-ylmethyl)urea (3bpmu), leading to the formation of two chain coordination polymers by adopting solution methods, namely, catena-poly[[[triaqua(5-amino-2,4,6-tribromoisophthalato-κO)cadmium(II)]-μ-3,3′-(diazene-1,2-diyl)dipyridine-κ2 N 1:N 1′] dihydrate], {[Cd(C8H2Br3NO4)(C10H8N4)(H2O)3]·2H2O} n or {[Cd(ATBIP)(mzpy)(H2O)3]·2H2O} n , (1), and catena-poly[[[tetraaquacadmium(II)]-μ-1,3-bis(pyridin-3-ylmethyl)urea-κ2 N 1:N 1′-[diaquabis(5-amino-2,4,6-tribromoisophthalato-κO)cadmium(II)]-μ-1,3-bis(pyridin-3-ylmethyl)urea-κ2 N 1:N 1′] octahydrate], {[Cd(C8H2Br3NO4)(C12H12N4O)(H2O)3]·4H2O} n or {[Cd(ATBIP)(3bpmu)(H2O)3]·4H2O} n , (2). Both complexes were characterized by FT–IR spectroscopic analysis, thermogravimetric analysis (TGA), solid-state diffuse reflectance UV–Vis spectroscopic analysis, and single-crystal and powder X-ray diffraction analysis (PXRD). The mzpy and 3bpmu ligands bridge the CdII metal centres in (1) and (2) into one-dimensional chains, and the ATBIP2− ligands show a monodentate coordination to the CdII centres in both coordination polymers. A discrete water tetramer exists in (1). Within the chains of (1) and (2), there are halogen bonds between adjacent ATBIP2− and mzpy or 3bpmu ligands, as well as hydrogen bonds between the ATBIP2− ligands and the coordinated water molecules. With the aid of weak interactions, the structures of (1) and (2) are further extended into three-dimensional supramolecular networks. An analysis of the solid-state diffuse reflectance UV–Vis spectra of (1) and (2) indicates that a wide indirect band gap exists in both complexes. Complexes (1) and (2) exhibit irreversible and reversible dehydration–rehydration behaviours, respectively, and the solid-state fluorescence properties of both complexes have been studied.


2015 ◽  
Vol 68 (6) ◽  
pp. 956 ◽  
Author(s):  
Ming-An Dang ◽  
Zi-Feng Li ◽  
Ying Liu ◽  
Gang Li

Three coordination polymers [Sr(p-H2MOPhIDC)2]n (1) (p-H3MOPhIDC = 2-p-methoxyphenyl-1H-imidazole-4,5-dicarboxylic acid), {[Cd2(p-HMOPhIDC)2(4,4′-bipy)]⋅H2O}n (4,4′-bipy = 4,4′-bipyridine) (2), and [Zn(p-HMOPhIDC)(4,4′-bipy)]n (3) have been solvothermally synthesized, and structurally characterized by single-crystal X-ray diffraction. Polymer 1 indicates a three-dimensional framework, which can be simplified as a 6-connected lattice. Polymer 2 is also a three-dimensional framework, and contains mixed bridging ligands HMOPhIDC2– and 4,4′-bipy. Polymer 3 exhibits a sheet structure bearing infinite rectangles. The coordination modes of the p-H3MOPhIDC ligand, and the thermal and solid-state photoluminescence properties of the polymers have been investigated as well.


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