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1.
Three new coordination polymers, [Zn(PBDC)(bbbm)0.5]n ( 1 ), [Co(PBDC)(bbbm)]n ( 2 ), and [Cd(PBDC)(bbbm)]n ( 3 ) were prepared via hydrothermal reactions of different metal(II) nitrates with flexible 1,3‐bis(4‐phenoxy)benzenedicarboxylic acid (H2L) and 1,1‐(1,4‐butanediyl)bis(benzimidazole) ligand. All these complexes were fully characterized by elemental analysis, FT‐IR, thermogravimetric analysis (TGA), powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Structure analyses revealed that complex 1 has a 2D→2D twofold interpenetrating framework simplified by a 4‐connected sql net with point symbol (44.62), whereas complexes 2 and 3 are isostructural and exhibit a 2D→2D twofold interpenetrating framework rationalized as a three‐connected hcb net with point symbol (63). Complexes 1 – 3 further expand to 3D supramolecular structures through non‐covalent C–H ··· O interactions. Additionally, the luminescent and magnetic properties of some of these complexes were studied. Complex 3 presents ideal photoluminescent behavior, whereas complex 2 shows antiferromagnetic coupling between the central CoII ions, suggesting its latent application in magnetic material.  相似文献   

2.
Two coordination polymers (CPs), {[Zn2(BMB)(5‐AIPA)2] · 2H2O}n( 1 ) and [Zn(BMB)(5‐NIPA)]n( 2 ) {BMB = 1, 4‐bis[(2‐methyl‐imidazol‐1‐yl)methyl]benzene, 5‐AIPA = 5‐aminoisophthalic acid, 5‐NIPA = 5‐nitroisophthalic acid}, were synthesized under hydrothermal conditions. Compound 1 displays a 2D double‐layer structure, which is packed into a 3D supramolecule by interlayer hydrogen bonds and π–π stacking interactions. Compound 2 displays a threefold interpenetrating 3D network, which is composed of left‐handed helical chains and two types of meso‐helical chains along different directions.  相似文献   

3.
Two new cobalt(II) coordination polymers, [Co(PDCO)(H2O)2]n ( 1 ) and [Co(PDCO)(bix)(2H2O)2·H2O]n ( 2 ) ( PDCO= pyridine‐2,6‐dicarboxylic acid N‐oxide, bix = 1,4‐bis(imidazol‐1‐ylmethyl)‐benzene) have been synthesized under hydrothermal conditions. Single‐crystal X‐ray analyses show that compound 1 is a 1D helical chainlike structure with 41 screw axes parallel to the crystallographic c‐axis and interchain hydrogen‐bonding interactions further result in a 3D framework; for compound 2 , each bix ligand connects two Co1 atoms (or two Co2 atoms) to give a zigzag chain structure and these 1D chains are connected by offset face‐to‐face π···π and hydrogen bond interactions to generate a 3D architecture. The thermogravimetric analyses were investigated for 1 and 2 . The determination of variable temperature magnetic susceptibilities indicates an antiferromagnetic interaction between the metal atoms for 1 and 2 .  相似文献   

4.
Investigating the coordination chemistry of H2CDA (4‐oxo‐1,4‐dihydro‐2,6‐pyridinedicarboxylic acid) with rare earth salts Ln(NO3)3 under hydrothermal conditions, structure transformation phenomenon was observed. The ligand, H2CDA charged to its position isomer, enol type structure, H3CAM (4‐hydroxypyridine‐2,6‐dicarboxylic acid). Six new lanthanide(III) coordination polymers with the formulas [Ln(CAM)(H2O)3]n [Ln = La ( 1 ), Pr, ( 2 )] and {[Ln(CAM)(H2O)3] · H2O}n [Ln = Nd, ( 3 ), Sm, ( 4 ), Eu, ( 5 ), Y, ( 6 )] were synthesized and characterized. The X‐ray structure analyses show two kinds of coordination structures. The complexes 1 and 2 and 3 – 6 are isostructural. Complexes 1 and 2 crystallize in the monoclinic C2/c space group, whereas 3 – 6 crystallize in the monoclinic system with space group P21/n. In the two kinds of structures, H3CAM displays two different coordination modes. The SmIII and EuIII complexes exhibit the corresponding characteristic luminescence in the visible region at an excitation of 376 nm.  相似文献   

5.
Two coordination polymers, namely [Zn(L)Cl] ( 1 ) and [Zn(L)2] ( 2 ) [L = 4‐(pyridin‐4‐ylmethoxy)benzolic acid] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction analyses, powder X‐ray diffraction, and thermogravimetric analysis. Compounds 1 and 2 have a two‐dimensional square‐shaped structure (the dimensions are 15.43 × 15.43 Å for 1 and 12.064 × 15.017 Å for 2 ) with (44 · 62) topology. Moreover, compounds 1 and 2 exhibit a 3D supramolecular structure made up by strong π–π interactions from the adjacent layers. Furthermore, compounds 1 and 2 show good fluorescence properties in the solid state at room temperature.  相似文献   

6.
The salen‐type ligand H2L [H2L = N,N′‐bis(salicylidene)‐1,2‐cyclohexanediamine] was utilized for the synthesis of two lanthanide(III) coordination polymers [LnH2L(NO3)3MeOH]n [Ln = Eu ( 1 ) and Ln = Lu ( 2 )]. The single‐crystal X‐ray diffraction analyses of 1 and 2 revealed that they are isomorphous and exhibit one‐dimension neutral structure, in which H2L effectively functions as a bridging ligand and give rise to a chain‐like polymer. The luminescent properties of polymers in solid state and in solution were investigated and 1 exhibits typical red luminescence of EuIII ions in solid state and dichloromethane solution and 2 emits the ligand‐centered blue luminescence. The energy transfer mechanisms in these luminescent lanthanide polymers were described through calculation of the lowest triplet level of ligand H2L.  相似文献   

7.
Three new coordination polymers, namely, [CuL0.5] ( 1 ), [Co(H2L)(H2O)2][H2O] ( 2 ), and [(CdCl)0.5Cd0.25(H2L)0.5] ( 3 ) were synthesized under hydrothermal conditions from the corresponding CuII, CoII, and CdII salts with a multidentate ligand of 2,2′,2′′,2′′′‐[2,3,5,6‐tetramethyl‐1,4‐phenylenebis(methylenenitrilo)]tetraacetic acid (H4L). The complexes were characterized by single‐crystal X‐ray diffraction, IR, thermogravimetric, and elemental analyses. Complex 1 crystallizes in the orthorhombic space group Pbca and has a three‐dimensional architecture with infinite two‐dimensional networks linked together by weak Cu–O interactions. Complex 2 crystallizes in the monoclinic space group P2(1) and displays a 2D network. Complex 3 crystallizes in the tetragonal space group P4(2)/ncm and exhibits an infinite 3D architecture that has unusual [Cd2(CO2)4Cl2] dinuclear paddle‐wheel units and [Cd(CO2)4] dodecahedron units. The results showed that the coordination arrangement of central metal atoms and the conformation and coordination mode of organic ligands play an important role in determining the structure of the complexes. The luminescence property of complex 3 was studied in the solid state at room temperature.  相似文献   

8.
在甲醇溶液中,将K2NiL·H2O和M(OAC)2(M = Co,Zn)按1:1的摩尔比进行组装反应,得到了镍、钴和镍、锌两种异金属一维链状配位聚合物,其化学组成分别为{[Ni2Co2L2(H2O)2]·CH3OH·3H2O}n(1)和{[Ni2Zn2L2 (H2O)2]·2CH3OH·H2O}n(2),(H4L=2-羟基-3-[(E)-({2-(2-羟基苯甲酰胺基)乙基}亚氨基)甲基]苯甲酸,OAC- = CH3COO-)。通过IR谱,元素分析的方法对其进行了表征,利用X-射线单晶衍射方法对其晶体结构进行了测定,结构分析表明:它们都是由不对称四核单元组成链状配位聚合物。  相似文献   

9.
Three ZnII and CdII complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L1)(2,2′‐bpy)2(H2O)] · 2H2O ( 1 ), [Zn(L1)(bpp)(H2O)] ( 2 ), and [Cd(L1)(H2O)] · H2O ( 3 ) [H2L1 = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.82). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated.  相似文献   

10.
Two coordination polymers [Zn2(ipt)2(CuL)2(H2O)] ( 1 ) and [Zn2(ipt)2(NiL)2(H2O)] ( 2 ) (ML, H2L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐dien; H2ipt = isophthalic acid) were synthesized by solvothermal methods and characterized by single‐crystal X‐ray diffraction. Complexes 1 and 2 exhibit ladderlike chains, consisting of Zn4Cu4 and Zn4Ni4 units, respectively, which are connected via oxamide and isophthalate. These chains are further interlinked by hydrogen bonds resulting in a 2D supramolecular architecture. The fluorescence properties of compounds 1 and 2 are also discussed.  相似文献   

11.
A series of five new ZnII and CdII mixed‐ligand coordination polymers, namely, {[Zn(L1)(4,4′‐bpy)] · (ClO4) · 2H2O} ( 1 ), {[Zn(L2)(4,4′‐bpy)0.5] · (ClO4)} ( 2 ), {[Zn(L3)(4,4′‐bpy)] · (NO3) · 2H2O} ( 3 ), {[Cd(L4)(4,4′‐bpy)0.5(NO3)] · 5H2O} ( 4 ), and {[Zn(L4)(4,4′‐bpy)] · Cl · H2O} ( 5 ) [4,4′‐bpy = 4,4′‐bipyridine, L1 = 4‐carboxy‐1‐(4‐carboxybenzyl)pyridin‐1‐ium chloride, L2 = 3‐carboxy‐1‐(4‐carboxybenzyl)pyridin‐1‐ium chloride, L3 = 4‐carboxy‐1‐(3‐carboxybenzyl)pyridin‐1‐ium chloride, and L4 = 3‐carboxy‐1‐(3‐carboxybenzyl)pyridin‐1‐ium chloride], were obtained by the reactions of the 4,4′‐bipyridine with four dicarboxylate zwitterionic pyridine ligands. Single‐crystal X‐ray structural analyses reveal that the five complexes demonstrate different molecular frameworks coming from various coordination modes and flexibilities of different dicarboxylate zwitterionic pyridine ligands and central metal atoms. Mononuclear twofold dinuclear 2D twofold interpenetrating net for 2 , four‐coordinate mononuclear twofold interpenetrating 2D layer for 3 , mononuclear 2D layer arranged in parallel and with large grids for 4 , and twofold trans interpenetrating 2D network for compound 5 . The structural diversities in 1 – 5 indicate that the nature of the ligands and the presence of different metal atoms have a great influence on central metal coordination modes and the structural topologies of the metal‐organic molecular architectures. In addition, π ··· π stacking interactions also play important roles in the final crystal packing and supramolecular frameworks. The powder X‐ray diffraction, elemental analysis, and photoluminescence properties of 1 – 5 were studied, which show that architectures play an important role in emission bands and intensities.  相似文献   

12.
Hydrothermal reactions of nickel or cobalt nitrate with the dipyridylamide ligand bis(4‐pyridylformyl)piperazine (4‐bpfp) and either 5‐methoxyisophthalate (H2omeip) or 5‐methylisophthalate (H2mip) afforded a series of coordination polymers that were structurally characterized by single‐crystal X‐ray diffraction. Different synthetic conditions afforded the 1D chain phase {[Ni(Homeip)2(H2omeip)(bpfp)] · 2H2O}n ( 1 ) or the mutually inclined interpenetrated (4, 4) grid system in {[Ni(omeip)(bpfp)(H2O)] · 2H2O}n ( 2 ). The analogous cobalt phase {[Co(omeip)(bpfp)] · 3H2O}n ( 3 ) lacks bound water molecules, which enforces a non‐interpenetrated (4, 4) grid structure based on {Co2(OCO)2} dinuclear clusters. Similar clusters are seen in {[Co(mip)(bpfp)(H2O)2] · 3.5H2O}n ( 4 ), which manifests a 1D ribbon structural motif. Its nickel congener {[Ni(Hmip)2(bpfp)(H2O)2] · 2H2mip}n ( 5 ) also shows a 1D chain motif. A variable temperature magnetic susceptibility study indicates antiferromagnetic coupling within the dimeric units in 3 and 4 concomitant with single ion effects. Additionally, thermal degradation properties of these new materials are described.  相似文献   

13.
A series of metal coordination polymers, [Co2(NB)4(bpp)2(H2O)]·H2O ( 1 ), [Co2(e,e‐trans‐chdc)(e,a‐cis‐chdc)(bpp)2] ( 2 ), [Ni(e,e‐trans‐chdc)(bpp)(H2O)2] ( 3 ), [Ni2(PDA)2(bpp)2(H2O)3]·H2O ( 4 ), and [Ni‐(mBDC)(bpp)] ( 5 ) (NB = 3‐nitrobenzoate anion; bpp = 4,4′‐trimethylene dipyridine; chdc = cyclohexane‐1,4‐dicarboxylate anion; PDA = 1,4‐phenylenediacetate anion; mBDC = 1,3‐benzene dicarboxylate anion), were synthesized from metal ions and organic mixed‐ligands by hydrothermal reactions. The single crystal structure analysis revealed that 1, 3, and 4 were 2D sheets with bilayer (1 and 4) and 2‐fold interpenetrated layers (3), 2 is a 3D binodal (4,5)‐connected framework, and 5 is a 1D chains. The non‐covalent interactions of H‐bonds and π–π stacking caused this conformation of highly cross‐linked networks. Compounds 1‐5 were further characterized by thermal gravimetric analysis, powder X‐ray diffraction, UV‐vis, infrared, and PL spectroscopy.  相似文献   

14.
Two trinuclear CoII and ZnII complexes, [(CoL)2(OAc)2Co] and [(ZnL)2(OAc)2Zn], with an asymmetric Salen‐type bisoxime ligand [H2L = 4‐(N,N‐diethylamine)‐2,2′‐[ethylenediyldioxybis(nitrilomethylidyne)]diphenol] were synthesized and characterized by elemental analyses, IR, UV/Vis, and fluorescent spectroscopy. The crystal structures of the CoII and ZnII complexes were determined by single‐crystal X‐ray diffraction methods. The CoII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in a trigonal bipyramid arrangement. With the help of intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions, a self‐assembled continual zigzag chain‐like supramolecular structure is formed. The ZnII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in an almost regular trigonal bipyramid arrangement. A self‐assembled continual 1D supramolecular chain‐like structure is formed by intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions. Additionally, the photophysical properties of the CoII and ZnII complexes were discussed.  相似文献   

15.
Cadmium(II) based 2D coordination polymer [Cd(L1)2(DMF)2] ( 1 ) (L1 = 4,5‐dicyano‐2‐methylimidazolate, DMF = N,N′‐dimethylformamide) and 2D cobalt(II)‐imidazolate framework [Co(L3)4] ( 2 ) (L3 = 4,5‐diamide‐2‐ethoxyimidazolate) were synthesized under solvothermal reaction conditions. The materials were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction measurement (PXRD) and single‐crystal X‐ray diffraction. Compound 1 has hexacoordinate CdII ions and forms a zigzag chain‐like coordination polymer structure, whereas compound 2 exhibits a 2D square grid type structure. The thermal stability analysis reveals that 2 showed an exceptional thermal stability up to 360 °C. Also, 2 maintained its fully crystalline integrity in boiling water as confirmed by PXRD. The solid state luminescent property of 1 was not observed at room temperature. Compound 2 showed an independent high spin central CoII atom.  相似文献   

16.
Two cobalt(II) coordination polymers, {[Co(μ‐4,4′‐bipy)(4,4′‐bipy)2(H2O)2]·(OH)3·(Me4N)·4,4′‐bipy·4H2O}n ( 1 ) and {[Co(μ‐4,4′‐bipy)(H2O)4]·suc·4H2O}n ( 2 ) (4,4′‐bipy = 4,4′‐bipyridine, suc = succinate dianions), were hydrothermally synthesized and structurally characterized by X‐ray diffraction analysis, UV‐Vis‐NIR, and ICP. The main structure feature common to the both polymers is presence of the infinite linear chains, [Co(μ‐4,4′‐bipy)(4,4′‐bipy)2(H2O)2]n ( 1 ) and [Co(μ‐4,4′‐bipy)(H2O)4]n ( 2 ), respectively. In 1 , the chains are further linked by the hydrogen‐bond and π‐π stacking interaction, producing extended layer structure. The 4,4′‐bipy molecules in 1 play three different roles. In 2 , the chains are linked into three‐dimensional network structure via complicated hydrogen bonding system. The variable temperature (2.0~300 K) magnetic susceptibility of 1 indicates a tendency of spin‐transition in the temperature range of 110 K to 22 K, which attributes to the transition of high‐spin to low‐spin from Co2+(d7) ion. Also, the result of surface photovoltage spectroscopy (SPS) reveals that the polymer 1 has significant photoelectric conversion property in the region of 300‐800 nm.  相似文献   

17.
Two coordination polymers, namely, {[Zn(bpea) (bmp)] · H2O}n ( 1 ) and {[Ni(bpea)(bimb)] · DMF}n ( 2 ) [H2bpea = biphenylethene‐4,4′‐dicarboxylate, bmp = 1,4‐bis(2‐methylimidazol‐3‐ium‐1‐yl)biphenyl and bimb = 1,4‐bis(1‐imidazol‐yl)‐2,5‐dimethyl benzene], were synthesized under solvothermal conditions with mixed organic ligands. Single crystal X‐ray diffraction reveals that complex 1 features a three‐dimensional (3D) structure with a sixfold interpenetrating dia net. Complex 2 shows a 3D fivefold interpenetrating dia topology. Furthermore, the solid state luminescent properties of complexes 1 and 2 were investigated at room temperature.  相似文献   

18.
Three new mixed‐ligand coordination polymers of CuII, namely, [Cu(Fbtx)(L1)(H2O)]n ( 1 ), [Cu(Fbtx)0.5(HL2)(H2O)2]n ( 2 ), and {[Cu(Fbtx)1.5(HL3)(H2O)] · H2O}n ( 3 ) [Fbtx = 2,3,5,6‐tetrafluoro‐1,4‐bis(1,2,4‐triazole‐1‐ylmethyl)benenze, H2L1 = terephthalic acid, H3L2 = trimesic acid, NaH2L3 = 5‐sulfoisophthalic acid monosodium salt], were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectra, and single‐crystal and powder X‐ray diffraction techniques. All the complexes have a two‐dimensional (2D) coordination layer structure. Of these, 1 displays a planar 44‐ sql structure whereas both 2 and 3 are highly undulated 63‐ hcb nets. Moreover, their thermal stability and catalytic behaviors in the aerobic oxidation of 4‐methoxybenzyl alcohol were also investigated as well. The results indicate that the benzene dicarboxylate ligands have an effective influence on the structures and catalytic properties of the resulting coordination polymers.  相似文献   

19.
Two new cobalt(II) coordination polymers, {[Co(L1)(tbta)] · 0.8H2O}n ( 1 ) and {[Co(L2)(tbta)] · H2O}n ( 2 ) [L1 = 1,1′‐(1,3‐propanediyl)bis(2‐methylbenzimidazole), L2 = 1,2‐bis(2‐methylbenzimidazole‐1‐ylmethyl)benzene, H2tbta = tetrabromoterephthalic acid] were obtained under hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction methods, IR spectroscopy, TGA, and elemental analysis. The cobalt atoms present similar environments with tetrahedral arrangements in 1 and 2 . The two complexes show a 2D (4,4) coordination network with sql topology. Compound 2 is further extended into a rare 3 , 3 , 4T3 three‐dimensional supramolecular framework by weak C–H ··· O hydrogen bonding interactions. The fluorescence and catalytic properties of the complexes for the degradation of the congo red azo dye in a Fenton‐like process were investigated.  相似文献   

20.
Two coordination polymers, namely Zn(HL)(4,4′‐bpy)1.5 ( 1 ), [Zn3(L)2(BIMB)2] · 5H2O ( 2 ) [H3L = 5‐(4‐carboxybenzyloxy)isophthalic acid, 4,4′‐bpy = 4,4′‐bipyridine, BIMB = 1,4‐bis(1H‐imidazol‐1‐yl)benzene] were synthesized under hydrothermal conditions. Their structures are determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and thermogravimetric (TG) analyses. Complex 1 features a 2D 4‐connected network. Complex 2 is a 3D twofold interpenetrating (3,4,6)‐connected net. In addition, the luminescent properties for 1 and 2 were studied in the solid state at room temperature.  相似文献   

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