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1.
Two new coordination polymers formulated as {[Zn(bdic)(bmt)H2O]?·?0.5H2O} n (1) and {[Cd(bdic)(bmt)(H2O)2]?·?2H2O} n (2) (H2bdic?=?1,3-benzenedicarboxylic acid, bmt?=?1-((benzotriazol-1-yl)methyl)-1-H-1,2,4-triazole) have been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Both coordination polymers exhibit 1-D chain structure where bmt is unidentate and bdic2? bridging. In 1, bmt hangs at two sides of the main chain, whereas bmt hangs at one side of the main chain in 2. Fluorescent properties have also been determined.  相似文献   

2.
Two 2-D Cd(II) complexes, {[Cd(imb)(bdc)(H2O)]·CH3OH}n (1) and {[Cd(imb)(Hbtc)(CH3OH)]·2H2O·CH3OH}n (2), have been synthesized by reactions of CdCl2·2.5H2O with 2-(1H-imidazol-1-methyl)-1H-benzimidazole (imb) and 1,3-benzenedicarboxylic acid (H2bdc) or 1,3,5-benzenetricarboxylic acid (H3btc). Single-crystal X-ray diffraction shows that 1 possesses an infinite 2-D layered structure in which all the carboxylates chelate Cd(II) and imb bridge Cd(II) ions. Complex 2 also features an infinite 2-D layered structure and imb ligands also bridge Cd(II) ions, but two carboxylates of each 1,3,5-benzenetricarboxylate coordinate to Cd(II) in monodentate or chelating mode, leaving the third one, which is not deprotonated, uncoordinated. IR spectra, fluorescent properties, and thermogravimetric analyses of both complexes have been investigated.  相似文献   

3.
Two new complexes, {[Cd(btec)0.5(imb)(CH3OH)]·CH3OH}n (1) and {[Cd(btec)0.5(H2btec)]·(H2imb)·2H2O}n (2) (H4btec = 1,2,4,5-benzenetetracarboxylic acid, imb = 2-(1H-imidazol-1-methyl)-1H-benzimidazole), have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Both complexes exhibit 2-D network structures. In 1, each 1,2,4,5-benzenetetracarboxylate links four Cd2+ cations, and each Cd2+ cation connects two 1,2,4,5-benzenetetracarboxylates, to form a 2-D layer, with the imb ligands located on each side of the 2-D layer. In 2, there are two kinds of 1,2,4,5-benzenetetracarboxylates in the structure. One kind is completely deprotonated and acts as hexadentate linkers, leading to a 2-D layer. The other kind is only doubly deprotonated and decorates each side of the 2-D layer. In 2, imb is protonated, forming (H2imb)2+ cations that only cocrystallize with the negatively charged Cd coordination polymer ({[Cd(btec)0.5(H2btec)]2?}n), but does not coordinate to the Cd2+ cations. IR spectra, PXRD patterns, thermogravimetric analyses, and fluorescent properties of 1 and 2 have also been determined.  相似文献   

4.
Two new complexes, {[Zn(imb)(SO4)]·H2O}n (1) and {[Cd2(imb)2(SO4)2(H2O)]·CH3OH}n (2) (imb?=?2-(1H-imidazol-1-methyl)-1H-benzimidazole), have been solvothermally synthesized. Single-crystal X-ray diffraction shows that 1 displays a 2-D (4,4) network, which is further extended to a 3-D supramolecular structure by hydrogen bonding interactions. Complex 2 exhibits a 3-D framework with (3,5)-connected (42·6)2(42·65·83)2 topology. The results indicate that changing metal ions can influence the coordination modes of sulfate, and then affect the structures of the complexes. In addition, IR and UV–vis spectra, powder X-ray diffraction patterns, thermogravimetric analyses, and fluorescent properties of both complexes have been investigated.  相似文献   

5.
Reactions of Zn(II) salts, 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (HIPT) and 2-mercaptobenzoic acid or 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H3PrIDC), result in two mixed-ligand coordination polymers (CPs), [Zn2(IPT)(DSDB)(OH)]n (H2DSDB = 2,2′-disulfanediyldibenzoic acid, 1) and [Zn2(IPT)(PrIDC)(H2O)]n (H3PrIDC = 2-propyl-1H-imidazole-4,5-dicarboxylic acid, 2). Compound 1 possesses a 2-D structure built by 1-D [Zn(IPT)]n chains and DSDB2? connectors, in which the DSDB2? is generated via in situ reaction from 2-mercaptobenzoic acid. It displays a new intricate 4-nodal {3·4·6·7·8·9}{3·6·7·8·9·10}{3·8·9}{4·6·8} topology. Compound 2 displays a 3-D framework with new 3-connected topology with Schläfli symbol of (4·8·10) (8·122), in which the 1-D Zn-carboxylate chains were bridged by 3-connected IPT? ligands. The thermal stabilities and luminescence properties of 1 and 2 have also been studied. The compounds exhibit intense solid-state fluorescent emissions at room temperature.  相似文献   

6.
Reactions of fresh M(OH)2 (M = Zn2+, Cd2+) precipitate and (RS)-2-methylglutaric acid (H2MGL), 2,2′-bipyridine (bipy), or 1,10-phenanthroline (phen) in aqueous solution at 50°C afforded four new metal–organic complexes [Zn2(bipy)2(H2O)2(MGL)2] (1), [Zn2(phen)2(H2O)(MGL)2] (2), [Cd(bipy)(H2O)(MGL)] · 3H2O (3), and [Cd(phen)(H2O)(MGL)] · 2H2O (4), which were characterized by single crystal X-ray diffraction, IR spectra, TG/DTA analysis as well as fluorescence spectra. In 1, the [Zn(bipy)(H2O)]2+ moieties are linked by R- and S-2-methylglutarate anions to build up the centrosymmetric dinuclear [Zn2(bipy)2(H2O)2(MGL)2] molecules. In 2, the 1-D ribbon-like chains [Zn2(phen)2(H2O)(MGL)2] n can be visualized as from centrosymmetric dinuclear [Zn2(phen)2(H2O)2(MGL)2] units sharing common aqua ligands. Both 3 and 4 exhibit 1-D chains resulting from [Cd(bipy)(H2O)]2+ and [Cd(phen)(H2O)]2+, respectively, bridged alternately by R- and S-2-methylglutarate anions in bis-chelating fashion. The intermolecular and interchain π···π stacking interactions form supramolecular assemblies in 1 and 1-D chains in 24 into 2-D layers. The hydrogen bonded lattice H2O molecules are sandwiched between 2-D layers in 3 and 4. Fluorescence spectra of 14 exhibit LLCT π → π* transitions.  相似文献   

7.
Four coordination polymers, [Zn(o-bdc)(bth)0.5(H2O)] n (1), [Cd(o-bdc)(bth)0.5(H2O)] n (2), [Zn(m-bdc)(bth)] n (3), and [Cd(p-bdc)(bth)?·?(H2O)2] n (4) (where o-bdc?=?1,2-benzenedicarboxylate, m-bdc?=?1,3-benzenedicarboxylate, p-bdc?=?1,4-benzenedicarboxylate, and bth?=?1,6-bis(triazol)hexane), have been hydrothermally synthesized and structurally characterized. Both 1 and 2 are isostructural, featuring two binodal architectures: (63)(65·8) topology in terms of o-bdc and ZnII/CdII as three- and four-connected nodes. Complex 3 shows a 2-D (4,4) network with the Zn?···?Zn?···?Zn angle of 57.84°, whereas 4 exhibits planar 2-D (4,4) network. These 2-D networks of 3 and 4 are extended by supramolecular interactions, such as CH?···?π/π–π stacking and hydrogen-bonding into 3-D architecture. A structural comparison of these complexes demonstrates that the dicarboxylate building blocks with different dispositions of the carboxyl site play a key role in governing the coordination motifs as well as 3-D supramolecular lattices. Solid-state properties such as photoluminescence and thermal stabilities of 14 have also been studied.  相似文献   

8.
Four Cd(II)- and Cu(II)-containing coordination polymers (CPs) based on a multidentate N-donor ligand and varied dicarboxylate anions, [Cd(3,3′-tmbpt)(p-bdc)]·2.5H2O (1), [Cd(3,3′-tmbpt)(m-bdc)]·2H2O (2), [Cu(3,3′-tmbpt)(m-bdc)]·H2O (3), and [Cu(3,3′-tmbpt)(p-bdc)]·2H2O (4), where 3,3′-tmbpt = 1 ? ((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, p-H2bdc = 1,4-benzenedicarboxylic acid, and m-H2bdc = 1,3-benzenedicarboxylic acid, have been prepared hydrothermally. The structures of the compounds were determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra and elemental analyses. Compound 1 exhibits a 3-D twofold interpenetrating framework with a 65·8 CdSO4 topology. Compound 2 is a 2-D layer containing meso-helical chains with a 44·62 sql topology. Compound 3 shows a 1-D → 3-D interdigitated architecture while 4 displays a 2-D → 3-D interdigitated architecture. The structural differences of the compounds indicate that the dicarboxylate anions and the central metal ions play important roles in the resulting structures of CPs. Optical band gaps and solid-state photoluminescent properties have also been studied.  相似文献   

9.
Three new coordination polymers, [Cu(butca)0.5(bipy)(H2O)] n · 2nH2O (1), [Zn(H2butca) (phen)(H2O)] n · nH2O (2), and [Cd(H2chhca)0.5(phen)(H2O)] n · 2nH2O (3) (H4butca =1,2,3,4-butanetetracarboxylic acid, H6chhca = 1,2,3,4,5,6-cyclohexanehexacarboxylic acid), were prepared and characterized by EA, IR, TG, and X-ray crystallography. Complex 1 is a 1-D double-chain coordination polymer in which tetradentate butca4? coordinates to four Cu(II) ions through four monodentate carboxylates. Complex 2 is a 1-D chain with tridentate H2butca2? coordinating to two Zn(II) ions through monodentate and chelating carboxylates. Complex 3 is a 1-D double-chain coordination polymer. H2chhca4? is octadentate coordinating to four Cd(II) ions through four chelating carboxylates. Hydrogen bonds and π–π stacking interactions play important roles in the formation of supramolecular architectures. The thermal stabilities of 13 show dehydrated coordination polymers are thermally stable in the range 260–400°C.  相似文献   

10.
Two complexes formulated as {[Cd(btec)0.5(tmb)H2O]·4H2O}n (1) and {[Cd(H2btec)(tmb)(H2O)]·2H2O}n (2) (H4btec?=?1,2,4,5-benzenetetracarboxylic acid, tmb?=?2-((1H-1,2,4-triazol-1-yl)methyl)-1H-benzimidazole) have been synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. Single crystal X-ray diffraction shows that 1 has a 2-D layer structure in which tmb bridges and all of the carboxylates from 1,2,4,5-benzenetetracarboxylate chelate. In 2 Cd(II) ions are bridged by monodentate carboxylates leading to a 2-D layer structure with all tmb ligands coordinated monodentate to Cd(II), hanging at two sides of the layers. Complexes 1 and 2 are further extended to 3-D supramolecular structures by hydrogen bonding interactions. Luminescent properties have been investigated in the solid state at room temperature.  相似文献   

11.
Three new complexes, [Cd(L)I2]2 (1), {[Cd(L)I2]?·?DMF} n (2), and [Cd2(L)4(μ 2-I)I(H2O)] n (3), have been obtained through self-assembly of an unsymmetrical ligand 2-(1H-imidazol-1-methyl)-1H-benzimidazole (L) with Cd(II) salts. Single-crystal X-ray diffraction shows that 1 displays a dimeric structure in which two Cd(II) ions are bridged by two bidentate bridging L. Complex 2 exhibits a 1-D chain structure (···Cd–L–Cd–L···) constructed by L bridging Cd(II) ions. In 3, the Cd(II) ions are five-connected nodes and linked by L and iodide leading to the 3-D network. Complexes 2 and 3 are synthesized maintaining the same solvents and stoichiometric ratio of metal and ligand at different reaction temperature. The different structures of the complexes indicate that the temperature plays a significant role in construction of the complexes. Luminescent properties of 13 have been investigated in the solid state at room temperature.  相似文献   

12.
Three new complexes: [Cd(btaa)(bipy)(CH3COO) · H2O] n (1), [Ni(btaa)2(H2O)4 · 6H2O] n (2), and [Mn(btaa)2(H2O)2] n (3) (bipy = 2,2′-bipyridine, Hbtaa = 1H-benzotriazole-1-acetic acid) were prepared and characterized by IR, elemental analyses, thermogravimetric analyses, and single-crystal X-ray analyses. In 1, cadmium ions are linked by btaa ligands into 1-D linear chains; the chains are extended into layers through C–H ··· O hydrogen bonds and π–π stacking interactions. Complex 2 is a mononuclear structure, extended to a 3-D network through multiple intermolecular hydrogen bonds. In 3, manganese is bridged by carboxylate groups of btaa in the syn–skew bidentate mode in two directions to form a 2-D grid-like framework with a (4, 4) topology. The solid-state fluorescence spectrum of 1 shows that the excitation peak is at 355 nm while the maximum emission peak is at 424 nm.  相似文献   

13.
Three complexes constructed with 2,2′-biphenyldicarboxylic acid, multidentate nitrogen donors, and metal salts, {[Cd(2,2′-dpdc)(tppp)(H2O)]2?·?2H2O} n (1), {[Pb(2,2′-dpdc)(pyphen)]2} n (2), and {[Pb(2,2′-dpdc)(dppz)]} n (3) (H2dpdc = 2,2′-diphenyldicarboxylic acid; tppp = 4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)phenol; pyphen?=?pyrazino[2,3-f]-[1,10]phenanthroline; and dppz = dipyrido[3,2-a:2′,3′-c]phenazine), are synthesized under hydrothermal conditions. These complexes are characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and photoluminescence. In 1, two 2,2′-dpdc ions bridge two Cd(II) ions to form an isolated cluster with Cd?···?Cd distance of 5.023(4)?Å. These clusters are further linked by intermolecular hydrogen bonds, yielding a 2-D supramolecular structure. Complex 2 contains two crystallographically independent Pb(II) ions in the asymmetric unit. Pb1 ions are bridged by 2,2′-dpdc anions to form a chain along the x-axis. Two Pb2 ions are coordinated by two 2,2′-dpdc anions and two pyphen ligands to form a cluster. These clusters are linked by π–π interactions to yield a 1-D supramolecular chain along the y-axis. In 3, neighboring Pb(II) atoms are bridged by 2,2′-dpdc anions to form a 1-D chain structure. Further, the chains are linked into a 3-D supramolecular network through aromatic π–π interactions.  相似文献   

14.
Three new coordination polymers, {[Cu(trza)(2,2′-bipy)(H2O)]?·?(ClO4)} n (1), {[Cu(trza)(2,2′-bipy)(H2O)]?·?(BF4)} n (2), and {[Cu(trza)(4,4′-bipy)]?·?(H2O)?·?(ClO4)} n (3) (Htrza?=?2-(1H-1,2,4-triazole)-1-acetic acid), have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 exhibit 1-D chain structure while 3 displays 2-D layer structure. The catalytic activities of 1 and 3 in the green oxidative coupling of 2,6-dimethylphenol have been investigated.  相似文献   

15.
Self-assembly of a flexible tripodal ligand, 1,3,5-tris(1,2,4-triazol-1-ylmethyl)benzene (ttmb) and organometallic carboxylate 1,1'-bis(3-carboxy-1-oxopropyl)-ferrocene (H2bfcs) with Cd(Ac)2?·?2H2O or CdCl2?·?2.5H2O yi elds two 2-D binodal (3,4)-connected complexes {[Cd2(bfcs)(Hbfcs)2(ttmb)2]?·?10H2O} n (1) and [CdCl(Hbfcs)(ttmb)] n (2), exhibiting the same topological type (42?·?6)(42?·?63?·?8). Both exhibit a layer structure, which is generated through 1-D undulated ladders connected by organometallic carboxylate, bfcs2? (in 1), or Cl? (in 2). Differential pulse voltammetry experiments indicate that half-wave potentials are slightly higher than that of H2bfcs. Both complexes exhibit similar weak fluorescent emissions at room temperature.  相似文献   

16.
Two complexes, [Cu2(TFSA)(2,2′-bpy)4]?·?TFSA?·?8H2O (1) and {[Cu(4,4′-bpy)(H2O)2]?·?TFSA?·?6H2O} n (2) (H2TFSA?=?tetrafluorosuccinic acid, 2,2′-bpy?=?2,2′-bipyridine, and 4,4′-bpy?=?4,4′-bipyridine), have been synthesized and structurally characterized by X-ray structural analyses. Complex 1 is a binuclear molecule bridged by TFSA ligands; 2 is a 1-D chain bridged by 4,4′-bpy ligands. The asymmetric units of the two complexes are composed of cationic complexes [Cu2(TFSA)(2,2′-bpy)4]2+ (1) and [Cu(4,4′-bpy)(H2O)2]2+ (2), free TFSA anion, and independent crystallization water molecules. A unique 2-D hybrid water–TFSA anionic layer by linkage of {[(H2O)8(TFSA)]2?} n fragments consisting of 1-D T6(0)A2 water tape and TFSA anionic units by hydrogen bonds in 1 was observed. Unique 2-D hybrid water–TFSA anionic layer generated by the linkage of {[(H2O)6(TFSA)]2?} n fragments consisting of cyclic water tetramers with appended water molecules and TFSA anionic units, and 1-D metal–water tape [Cu–H2O?···?(H2O)6?···?H2O?] n in 2 were found. 3-D supramolecular networks of the two complexes consist of cationic complexes and water–TFSA anionic assemblies connected by hydrogen bonds.  相似文献   

17.
Three Cu(II) complexes, Cu2(bpy)(H2O)(Clma)2 (1), Cu2(bpe)(H2O)2(Clma)2 (2), and Cu(bpp)(Clma) (3), were synthesized (HClma = (R)-2-Chloromandelic acid, bpy?=?4,4′-dipyridine, bpe?=?1,2-di(4-pyridyl)ethylene, bpp?=?1,3-di(4-pyridyl)propane). Complexes 1, 2, and 3 are constructed from 1-D coordination arrays generated from Cu2(H2O)(Clma)2, Cu2(H2O)2(Clma)2, and Cu2(Clma)2 moieties and linked through bpy, bpe, and bpp co-ligands, respectively. 1 and 2 are assembled into 3-D supramolecular networks via O–H?O hydrogen bonds with topology of (63)(69·8) and (412·63), respectively, and 3 is assembled into a 3-D architecture through C–H?O hydrogen bonds with topology of (43·63)(43)(44·65·8)(46·66·83). Compounds 1, 2, and 3 crystallized in acentric space groups P21, P1, and P21, which exhibit significant ferroelectricity (remnant polarization Pr?=?0.008?μC?cm?2, coercive field Ec?=?21.4?kV?cm?1, the spontaneous saturation polarization Ps?=?0.167?μC?cm?2 for 1, Pr?=?0.183?μC?cm?2, Ec?=?1.69?kV?cm?1, and Ps?=?0.021 μC?cm?2 for 3). Results from infrared and thermal analyses are also discussed.  相似文献   

18.
Three new Zn(II) complexes, [Zn(ox)(imb)] (1), [Zn2(mal)2(imb)2] (2), and [Zn(suc)(imb)]·H2O (3) (imb = 2-(1H-imidazolyl-1-methyl)-1H-benzimidazole, H2ox = oxalic acid, H2mal = malonic acid, H2suc = succinic acid), have been synthesized and structurally characterized. Complex 1 is a 3-D framework with a 4-connected diamond topology with the topological notation of 66. Complex 2 exhibits 2-D layers with (6,3) networks. Complex 3 displays a 3-D framework constructed through unusual 2-D → 3-D parallel interpenetration of corrugated 2-D (6,3) networks. IR spectra, PXRD patterns, thermogravimetric curves, and photoluminescence spectra are addressed.  相似文献   

19.
Two new coordination compounds, {[Cd2(btrm)(ip)2(H2O)2]?·?2H2O} n (1) and {[Cd2(btrm)(hip)2(H2O)4]?·?3H2O} n (2) (btrm?=?bis(1,2,4-triazol-1-yl)methane, H2ip?=?isophthalic acid, H2hip?=?5-hydroxy isophthalic acid), have been synthesized and structurally characterized. Compound 1 is a 3-D network with CdSO4 topology. Compound 2 contains 1-D ladder structures, which are interconnected by classical hydrogen-bonding interactions (O–H?···?O) to lead to 3-D supramolecular architectures. Luminescence was performed on 1 and 2, both of which showed strong fluorescent emissions in the solid state at room temperature.  相似文献   

20.
Four copper(II) complexes and one copper(I) complex with pyridine-containing pyridylalkylamide ligands N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide (HLpz) and N-(2-(pyridin-2-yl)ethyl)pyrazine-2-carboxamide (HLpz?) were synthesized and characterized. The X-ray crystal structures of [Cu2(Lpz)2(4,4?-bipy)(OTf)2] (1, OTf?=?trifluoromethanesulfonate, 4,4?-bipy?=?4,4?-bipyridine) and [Cu(Lpz)(py)2]OTf·H2O (2, py?=?pyridine) revealed binuclear and mononuclear molecular species, respectively, while [Cu(Lpz)(μ2-1,1-N3)]n (3), [Cu(Lpz?)(μ2-1,3-N3)]n (4), and [Cu(HLpz)Cl]n (5) are coordination polymer 1-D chains in the solid state.  相似文献   

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