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1.
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   

2.
Four new complexes, [Cu(L)] (1), [Cu2(L)(dpe)0.5]?·?2.5H2O (2), [Mn(L)] (3), and [Mn(L)(pybim)] (4) [H2L?=?5-(benzimidazol-1-ylmethyl)isophthalic acid, dpe?=?1,2-di(pyridin-4-yl)ethylene, pybim?=?2-(pyridin-2-yl)-1H-benzimidazole], have been synthesized under hydrothermal conditions and characterized by single-crystal and powder X-ray diffractions, FT-IR, and elemental analysis. The crystal structural analyses reveal that 1 and 4 are uninodal 3-connected 2-fold interpenetrated 2-D networks with (63) topology, 2 shows an infinite 1-D double-stranded chain structure, and 3 exhibits a uninodal 4-connected 2-D network with (44?·?62) topology. The factors influencing the structures of the coordination polymers are discussed. In addition, the thermal stabilities of 14, second-order non-linear optical effect of 1, and preliminary magnetic property of 3 have also been investigated.  相似文献   

3.
Two new compounds, [Cd2(bptc)(bpimb)(H2O)]?·?2H2O (1) and [Cd2(bptc)(bpib)]?·?4H2O (2) (where H4bptc?=?biphenyl-3,3′,4,4′-tetracarboxylic acid, bpimb?=?1,3-bis((2-(pyridin-2-yl)-1H-imidazol-1-yl)methyl)benzene, bpib?=?1,4-bis(2-(pyridin-2-yl)-1H-imidazol-1-yl)butane), were synthesized by reactions of the corresponding metal salts with H4bptc and N-containing auxiliary ligands and their structures have been determined by single-crystal X-ray diffraction. Compound 1 is built by Cd4-clusters which further construct a 3-D (3,8)-connected framework with tfz-d notation; 2, also built by Cd4-clusters, is a 3-D (4,8)-connected framework with (32?·?42?·?52)(34?·?48?·?512?·?64) topology. In addition, the elemental analyses, infrared spectra, fluorescence, and thermogravimetric analyses for 1 and 2 are discussed.  相似文献   

4.
Two Ni(II) metal–organic frameworks, [Ni(INAIP)(DMF)]·0.5DMF and [Ni(INAIP)(H2O)]·2H2O, have been synthesized by the reaction of 5-(isonicotinamido)isophthalic acid (H2INAIP) with NiSO4·6H2O using different reaction solvents. Single-crystal X-ray diffraction analysis indicates that [Ni(INAIP)(DMF)]·0.5DMF has a twofold interpenetrated three-dimensional (3D) framework with sra topology, while [Ni(INAIP)(H2O)]·2H2O has a two-dimensional (2D) network structure with a 4-connected (43·63) topology. In addition, the magnetic and adsorption properties of the complexes were explored.  相似文献   

5.
Two 3-D MOFs, {[Co2(oba)2(bmip)]·DMA}n (1) and [Cd(1,3-bdc)(bmip)]n (2), where H2oba = 4,4′-oxybis(benzoic acid), 1,3-bdc = isophthalic acid and bmip = 1,3-bis(2-methylimidazolyl)propane, were synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, FT-IR, TGA, and elemental analysis. Complex 1 features a 3-D→3-D twofold interpenetrating framework, and topological analysis shows the framework can be described as a 6-connected uninodal pcu net having the point symbol (412.63). Complex 2 shows a 3-D→3-D threefold interpenetrating network that can be described as a 4-connected uninodal cds net with (65.8) topology. Gas adsorptions of 1 were carried out, and photoluminescent properties of 1 and 2 were also investigated at room temperature.  相似文献   

6.
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   

7.
Two coordination polymers, namely [Ni(L1)-(ndc)(H2O)] n (1) and [Cu(L2)0.5(ndc)] n (2) (L1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, L2 = 1,4-bis(2-methylbenzimidazole)butane, H2ndc = 2,6-naphthalenedicarboxylic acid) have been synthesized and characterized by single-crystal and powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and elemental analysis. Complex 1 features a 2D 3-connected hcb network with 63 topology, which is further extended into a 3D supramolecular framework by O–H···O hydrogen bonding interactions. Complex 2 possesses a 3D threefold interpenetrating (4,5)-connected xah topological network, and its Schläfli symbol is (42.62.82)(46.64). Both complexes exhibit intense luminescence emissions in the solid state and promising catalytic activities for the degradation of Congo red azo dye in a Fenton-like process.  相似文献   

8.
Two pairs of isostructural transition metal coordination polymers, {[Co(L)(H2O)]n} (1) and {[Zn(L)(H2O)]n} (3), {[Co(L)(4,4′-bipy)(H2O)]·H2O}n (2) and {[Zn(L)(4,4′-bipy)(H2O)]·H2O}n (4) (H2L = N-pyrazinesulfonyl-glycine acid and 4,4′-bipy = 4,4′-bipyridine), have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental and thermogravimetric analyses. The structures show that 1 and 3 display 2-D polymeric grid frameworks with a 3-connected (4, 82) topology. 2 and 4 also exhibit a 2-D polymeric grid structure, but are constructed by a 4-connected (4, 4) topology. The adjacent 2-D polymeric grid frameworks for 1–4 are further linked by hydrogen bonding O–H?O interactions to form 3-D supramolecular interweaved orderly networks. The fluorescent properties of 3 and 4 were investigated in the solid state.  相似文献   

9.
Five new divalent metal coordination polymers containing either 1,3‐adamantanedicarboxylate (adc) or 1,3‐adamantanediacetate (ada) and pillaring dipyridyl ligands were prepared and structurally characterized by single‐crystal X‐ray diffraction. Using the V‐shaped linker 4,4′‐dipyridylamine (dpa), three new phases were isolated. {[Zn2(ada)2(dpa)2] · 4.5H2O}n ( 1 ) shows a (4,4) grid topology with embedded octameric water clusters. {[Co(ada)(dpa)(H2O)] · H2O}n ( 2 ) also manifests a 2D dimensionality, but with an intriguing novel (4)(12)(4.125) looped topology. {[Cd(adc)(H2O)2] · H2O}n ( 3 ) did not incorporate dpa ligands during self‐assembly, but exhibits an uncommon 3‐connected 83 etb network topology. [Co(ada)(ebin)]n ( 4 ) [ebin = ethanediaminebis(nicotinamide)] possesses a (3,6) triangular net based on {Co2(OCO)2} dimeric units. {[Cd(adc)(ebin)] · 2H2O}n ( 5 ) also shows dimeric units, although linked into a decorated (4,4) grid topology. Magnetic susceptibility studies of compound 4 revealed a decrease in χmT product upon cooling, ascribed to antiferromagnetic coupling concomitant with single‐ion effects [g = 2.39(2) with D = 40(3) cm–1 and J = –3.55(4) cm–1]. Compounds 1 and 5 undergo blue‐violet fluorescence upon ultraviolet irradiation; the zinc derivative 1 shows potential as a sensor for the solution‐phase detection of nitrobenzene and m‐nitrophenol. Thermal decomposition behavior of the five new phases is also discussed.  相似文献   

10.
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   

11.
《Journal of Coordination Chemistry》2012,65(16-18):2691-2701
Abstract

A luminescent metal-organic framework, [Cd(tmlb)(bbibp)]n (1) (H2tmlb?=?(1H-1,2,4-triazol-1-yl)methylenebis(benzonic acid), bbibp?=?bis(benzoimidazo-1-ly)biphenyl), has been solvothermally synthesized and characterized by elemental analysis, infra-red spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis, and powder X-ray diffraction. Complex 1 exhibits two interpenetrating uninodal 4-connected 3-D frameworks with a (65·8) topology. The luminescence studies reveal that the complex displays sensitive and selective luminescence sensing toward Cr(VI) (CrO42? and Cr2O72?) anions, Fe(III) cation, and nitrobenzene. The potential quench mechanism was discussed.  相似文献   

12.
Two new coordination polymers, formulated as [Co(L1)(btec)0.5] n (1) and {[Co(L2)(bdc)]·H2O} n (2) (L1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2bdc = 1,3-benzenedicarboxylic acid, H4btec = 1,2,4,5-benzenetetracarboxylic acid, L2 = 1,3-bis(benzimidazol-1-ylmethyl)benzene), have been hydrothermally synthesized and characterized by physicochemical and spectroscopic methods as well as single-crystal X-ray diffraction. The cobalt atoms present different environments, with a trigonal pyramidal geometry in 1 and a distorted octahedral configuration in 2. Complex 1 shows a 2D (4,4) network linked by L1 and btec4? anions, giving an uninodal 4-connected sql topology with a point symbol of {42·62}, while complex 2 displays a 1D ladder-like chain structure, which is further assembled into a 3D supramolecular architecture via C–H···π hydrogen bonding interactions. The fluorescence properties of both complexes have been investigated in the solid state.  相似文献   

13.
Two new organic–inorganic polyoxometalates [Cu(dien)(H2O)]2{[Cu2(dien)2(OH)]2[Cu4(B-α-XW9O33)2]}·4H2O (X?=?Sb, 1; X?=?As, 2) (dien?=?diethylenetriamine) were hydrothermally synthesized and characterized by elemental analysis, IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. Both compounds are constructed from one four-coordinate [Cu(dien)(H2O)]2+, one {[Cu2(dien)2(OH)]2[Cu4(B-α-XW9O33)2]} building unit, and four water molecules of crystallization. Structural analysis shows that the sandwich-like polyoxotungstate cluster anions [Cu4(B-α-XW9O33)2]10? are linked by six adjacent dimeric cations [Cu2(dien)2(OH)]3+ into a 2-D architecture with a (6,3)-connected topology. Magnetic measurements of 1 and 2 exhibit the presence of antiferromagnetic interactions within the tetranuclear-CuII cluster.  相似文献   

14.
Abstract. The 3D cobalt(II) coordination polymers [Co1.5(HDDB)(1,4‐bib)1.5(H2O)]n ( 1 ), and {[Co2(DDB)(1,3‐bib)22‐H2O)] · H2O}n ( 2 ) were assembled by mixed‐ligand synthetic strategy [H4DDB = 1,3‐bis(2,4‐dicarboxyphenyl) benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and 1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene]. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. Single X‐ray diffraction analysis reveals that complex 1 is an interestingly 3D (3,3.6)‐connected (63)4(65 · 88 · 102) net, and complex 2 is an unprecedented dinuclear [Co2(COO)(μ2‐H2O)] SBUs based 3D (3,6)‐connected (3 · 6 · 7)(32 · 43 · 54 · 63 · 7 · 82) net. Additionally, the magnetic properties of 2 were investigated.  相似文献   

15.
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   

16.
Three coordination polymers, namely {[Ni(L1)(nip)(H2O)]·2H2O} n (1), [Co(L2)(tbip)] n (2), and {[Co2(L3)2(bptc)]·3H2O} n (3) (L1 = 1,4-bis(5,6-dimethylbenzimidazole)butane, L2 = 1,4-bis(5,6-dimethylbenzimidazole)-2-butylene, L3 = 1,3-bis(5,6-dimethylbenzimidazole)propane, H2nip = 5-nitro-isophthalic acid, H2tbip = 5-tert-butyl-isophthalic acid, H4bptc = biphenyl-3,3′,4,4′-tetracarboxylic acid), have been synthesized under hydrothermal conditions and characterized by physicochemical and spectroscopic methods as well as by single-crystal X-ray diffraction analysis. Complexes 1 and 2 both feature a two-dimensional (4,4) layer with (44 × 62) topology. Complex 3 possesses a uninodal 4-connected 2D htb network. The fluorescence spectra and catalytic properties of the complexes for the degradation of methyl orange by sodium persulfate in a Fenton-like process are reported.  相似文献   

17.
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   

18.
Two dinuclear Fe(III) metal–organic complexes with tetracarboxylate and chelating N-donor ligands, [Fe(Hbtec)(phen)(H2O)]2·2H2O (1) and [Fe(Hbtec)(bpy)(H2O)]2·2H2O (2) (H4btec = 1,2,3,5-benzenetetracarboxylic acid, phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine) have been prepared and characterized by elemental analysis, IR spectroscopic, and X-ray diffraction methods. Both complexes crystallize in the monoclinic space group P21/c with two Fe(III) ions bridged by two Hbtec3? ligands into a dinuclear unit. Hydrogen bonding connects the dinuclear units into a 3-D framework. The dinuclear units are 10-connected nodes that produce a 3-D framework with topology Schläfli symbol as (312·428·55). Thermal stabilities and luminescent properties of the two complexes have also been investigated.  相似文献   

19.
Six new coordination complexes, [Cd(η 2-OOCCH=(CH3)CFc)2(bix)]2·(CH3OH)0.5 (1), [Zn(η 2-OOCCH=(CH3)CFc)(η 1-OOCCH=(CH3)CFc)(bix)]2·(H2O)0.5 (2), [Zn(η 2-OOCCH=(CH3)CFc)2(pbbm)]2·(CH3OH)2 (3), {[Mn(η 1-OOCCH=(CH3)CFc)2(bbbm)(H2O)2]·(CH3OH)3}n (4), {[Cd(η 1-OOCCH=(CH3)CFc)2(bbbm)]·(CH3OH)2}n (5), and [Cd(η 2-OOCCH=(CH3)CFc)2(pmbbm)]n (6) {Fc?=?(η 5-C5H4)Fe(η 5-C5H4), bix?=?1,4[bis(imidazol-1-ylmethyl)benzene], pbbm?=?1,1′-[(1,4-propanediyl)bis-1H-benzimidazole], bbbm?=?1,1′-[(1,4-butanediyl)bis-1H-benzimidazole)], pmbbm?=?1,1′-[(1,4-pentanediyl)bis-1H-benzimidazole]}, were prepared and characterized. X-ray crystallographic analysis reveals that 1–3 are dimers bridged by bix and pbbm. Complexes 4–6 are one-dimensional (1-D) structures bridged by bbbm and pmbbm, respectively. Various ππ interactions were discovered in 1–6 that make significant contributions to molecular self-assembly. Solution differential pulse voltammetry of 1–6 indicates that the half-wave potentials of the ferrocenyl moieties in these complexes shift to positive potential compared with that of 3-ferrocenyl-2-crotonic acid.  相似文献   

20.
In the presence of Cu(II) ions, a chiral rare earth iodate Gd(IO3)3?·?H2O (crystallizing in P21 (no. 4) space group), was synthesized hydrothermally from Gd2O3 and HIO3; the structure is the topologically (3,?8)-connected (43)(4?·?62)(49?·?617?·?82) network, constructed from 3-connected trigonal nodes (I1, I3) and 8-connected tetragonal prism nodes (Gd1).  相似文献   

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