Synthesis,Structure and Magnetic Property of a New Three-dimensional Copper(Ⅱ) Coordination Polymer Constructed from 5-Tert-butyl Isophthalic Acid and N-donor Ligand

A new 3D copper(Ⅱ) coordination polymer, {[Cu_2(tbip)_2(1,3,5-tib)]×2H_2O}n(1, H_2 tbip = 5-tert-butyl isophthalic acid, 1,3,5-tib = 1,3,5-tris(1-imidazolyl)benzene), has been synthesized by hydrothermal reaction of Cu(OAc)_2·4H_2O, H_2 tbip and 1,3,5-tib. It has been structurally characterized by element analysis, IR and magnetic measurement. X-ray single-crystal analysis was carried out for 1, which crystallizes in the triclinic system, space group P1 with a = 7.822(3), b = 15.854(6), c = 17.553(6) ?, a = 113.033(4), β = 90.694(4), g = 101.006(4)°, V = 1957.3(12) ?~3, Z = 1, D_c = 1.493 g/cm~3, M_r = 1759.70, F(000) = 908, R = 0.0721 and w R = 0.1978 with I 2s(I). The single-crystal X-ray diffraction studies reveal that compound 1 exhibits 2D [Cu(tbip)] layers which are further pillared by 1,3,5-tib ancillary ligand with terminal tridentate coordination mode to generate the final 3D structure. Magnetic susceptibility data for 1 have been measured in the range of 2~300 K. There are antiferromagnetic interactions between copper ions of the compound.     

Syntheses and Structures of a New Tetrazylphosphonate Ligand and the Coordination Polymer Based on Zn~(Ⅱ)

A novel tetrazylphosphonate ligand, namely ethyl 4-(2-ethyl-2H-1,2,3,4-tetrazol-5-yl) benzylphosphonate(Et-L), was designed and successfully achieved from p-cyano benzyl chloride, based on which a zinc coordination polymer(1) with a 2D layer structure has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TGA and X-ray single-crystal diffraction. The colorless block crystals of H_2L·H_2O were also obtained under the same hydrothermal conditions, which belongs to monoclinic system, space group P2_1/c with a = 13.3141(7), b = 5.1650(3), c = 21.9839(18) ?, β = 115.307(5)°, V = 1366.69(15) ?~3, Z = 4, D_c = 1.391 mg/cm~(-3), Mr = 349.58, F(000) = 600, R = 0.0748 and wR = 0.1917 for 2392 observed reflections(I 2σ(I)). The colorless block crystals of complex 1([Zn(L)(H_2O)]_n) also belong to monoclinic system, space group P2_1/c with a = 22.7464(10), b = 6.0430(3), c = 9.7704(4) ?, β = 92.525(4)°, V = 1341.70(10) ?~3, Z = 4, D_c = 1.731 mg/cm_(-3), M_r = 349.58, F(000) = 712, R = 0.0596 and wR = 0.1688 for 2357 observed reflections(I 2σ(I)). Only the oxygen atoms of phosphonic group are coordinated with the metal zinc probably because the hydrogen atom of tetrazole has been substituted by ethyl group. Photoluminescence properties of the complex are also investigated.     

A Novel Zn(Ⅱ)Complex with 1D Supramolecular Water Tape Formed by Cyclic Tetrameric Water Clusters

<正>A new mixed-ligand Zn(Ⅱ)complex,[Zn(4,4'-bipy)_2(H_2O)_4]·2ANS·6H_2O(1,4,4'- bipy=4,4'-bipyridine,HANS=2-aminonaphthalene-1-sulfonic acid),has been isolated and structurally characterized by single-crystal X-ray diffraction,FT-IR spectrum,TG and elemental analysis.It crystallizes in the monoclinic system,space group P2_l/c with a=12.4852(8),b= 18.3163(12),c=10.9707(7)(?),β=114.2600(10)°,V=2287.3(3)(?)~3,D_c=1.455 g/cm~3,M_r= 1002.37,Z=2,F(000)=1048,μ=0.704 mm~(-1),the final R=0.0408 and wR=0.962 for 4029 observed reflections with I2σ(I).Interestingly,an unusual one-dimensional(1D)water tape with cyclic tetrameric water clusters can be observed in 1,which are further trapped via Zn-O coordination bonds exhibiting a 2D Zn(Ⅱ)-water layer.These 2D Zn(Ⅱ)-water layers are stacked together into a 3D interdigitated supramolecular architecture via weakπ…πinteractions,in which free ANS anions are tightly filled by hydrogen-bonding interactions.Thus,π…πand classical hydrogen-bonding interactions are found as main driving forces to stabilize the 2D Zn(Ⅱ)-water layers.     

Synthesis and Crystal Structure of a New Zinc(Ⅱ) Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol) Ligands

A new complex [Zn(4-nph)(bib)]_(2n)·nH_2O(1) has been obtained by the reaction of metal(Zn(Ⅱ)),1,4-bis(imidazol-1-yl)-butane(bib) with 4-nitrophthalic acid(4-H_(2nph)).The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 ?,α = 88.487(3),β = 72.529(3),γ = 79.991(3)°,V = 2009.8(5) ?~3 and Mr = 945.47.Complex 1 shows a three-dimensional(3 D) framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.     

Synthesis,Structure and Luminescent Property of a New Zn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylate and 4,4'-Bipyridine Ligands

A new Zn(II) coordination polymer [Zn3(BTC)2(4,4'-bpy)(CO)2]n(1, H3 BTC =1,3,5-benzenetricarboxylic acid, 4,4'-bpy = 4,4'-bipyridine) has been prepared through urothermal reaction of zinc nitrate hexahydrate with 1,3,5-benzenetricarboxylic acid and 4,4'-bipyridine, and characterized by elemental analysis, IR spectroscopy, TGA and powder XRD, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group C2/c, with a = 10.262(3), b = 18.838(5), c =15.083(4) A, β = 99.203(4)o, V = 2878.3(14) A3, C30H14Zn3N2O14, Mr = 822.54, Z = 4, Dc = 1.898g/cm3, μ = 2.561 mm-1, F(000) = 1640, R = 0.0363 and w R = 0.0932 for 2828 observed reflections(I 2σ(I)). X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn(II) atoms which are connected by BTC3- ligands and 4,4'-bpy coligands to form a 3D framework with 1D channels. The solid luminescence of ligand and the title complex was also studied at room temperature.     

Crystal Structure and Luminescent Properties of a 3D Cd(Ⅱ) Compound Constructed from Succinate and 3,6-Di(4-pyridyl)pyridazine

A three-dimensional(3D) coordination polymer,[Cd(SC)(DPPD)]_n(1,H_2SC = succinic acid and DPPD = 3,6-di(4-pyridyl)pyridazine),has been synthesized by the solvothermal reaction of Cd(NO_3)_2·4H_2O with H_2 SC and DPPD at 120 oC in DMF solvent. Compound 1 crystallizes in the monoclinic system,space group P2_1/c,with a = 10.7993(4),b = 11.7705(3),c = 13.5336(6) ?,V = 1678.89(11) ?~3,Z = 4,C18H14N4O_4 Cd,M_r = 462.73,D_c = 1.831 g/cm~3,μ = 1.335 mm~(-1),F(000) = 920.0,the final R = 0.0500 and wR = 0.1567 for 3714 observed reflections with I 2s(I). In compound 1,the Cd(Ⅱ) ions are linked by the SC~(2–) ligands to give a two-dimensional(2D) undulating sheet based on the centrosymmetric dinuclear Cd_2(COO)_2 units. The 2D sheets are further connected by the DPPD ligands to produce a 3D structure,which is a 6-connected(4~4·6·~(10)·8) topological network based on the dinuclear Cd_2(COO)_2 node. Compound 1 exhibits a photoluminescent emission with a maximum at 540 nm upon excitation at 460 nm.     

Effect of pH/Auxiliary Ligand on the Structures of Coordination Compounds Based on a Novel Ligand 2,6-Bis(pyrazin-2-yl)pyridine-4-carboxylate

Four new coordination compounds, [Zn(bppc)_2(H_2O)_2]·3 H_2O(1), [Zn2(bppc)2(mbdc)(H_2O)4]·7 H_2O(2), [Zn(bppc)2(H_2O)2]n·n(m-Hbdc)·n(H_2O)(3), [Zn2(bppc)(btc)(H_2O)3]n·5 n H_2O(4)(Hbppc = 2,6-bis(pyrazin-2-yl)pyridine-4-carboxylate, H2(m-bdc) = 1,3-benzenedicarboxylic acid, H3 btc = 1,3,5-benzene-tricarboxylic acid), have been hydrothermally synthesized and structurally characterized. Compound 1 shows a mononuclear structure and 2 shows a dinuclear structure. Compound 3 is a one-dimensional chain structure, which is extended into a 3D supramolecular network by intermolecular hydrogen interactions. In 4, a 1D loop-like chain is connected by(btc)3-anions to generate a 2D layer structure. The structure differences of 1~4 show that the p H and aromatic acid as auxiliary ligand have important influence on the final structures.iAdditionally, the luminescent properties of 1~4 have been investigated with fluorescent spectra in the solid state, and 1~4 display a strong fluorescent emission at room temperature and have potential applications as fluorescent-emitting materials.     

A New Zn(Ⅱ) Coordination Polymer Constructed from 1,3,5-Benzenetricarboxylate Ligand Exhibiting Photoluminescence

The title Zn(II) coordination polymer {[Zn_2(BTC)(HBTC)(dpa)(Hdpa)]·3H_2O}_n(1,H_3BTC = 1,3,5-benzenetricarboxylic acid,dpa = 4,4?-dipyridylamine),has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder X-ray diffraction,IR spectroscopy and Fluorescence spectroscopy.Complex 1 belongs to the triclinic system,space group P1,a = 9.9415(4),b = 13.5859(8),c = 15.2987(5) ?,α = 96.301(4),β = 107.944(3),γ = 103.575(4)°,V = 1873.48(14) ?~3,Z = 2,μ = 1.365 mm~(-1),Dc = 1.672 g/cm~3,Mr = 943.44,F(000) = 964,the final R = 0.0314 and wR = 0.0710 with I 2σ(I).Complex 1 displays a two-dimensional bilayer coordination polymer.Complex 1 shows fluorescence in the solid state at room temperature.     

Syntheses,Crystal Structures and Luminescent Properties of Two New Zinc(Ⅱ) Complexes Based on Bifunctional Ligand

By using solvothermal method,two novel coordination polymers based on 4-(4-carboxyphen-yl)-1,2,4-triazole(Hcpt) and Zn(Ⅱ) cations,[Zn(cpt)(OH)]_n·n H_2O(FJU-32) and [Zn(cpt)(atrz)]n(FJU-33)(Hatrz = 3-amino-1,2,4-triazolate),were synthesized and characterized by single-crystal X-ray diffraction analyses,elemental analyses,FT-IR and powder X-ray diffraction. FJU-32 crystallizes in monoclinic,space group P21/c with a = 3.7441(3),b = 23.0384(19),c = 11.8562(10) ?,β = 99.069(8)o,V = 1009.91(15) ?3,Dc = 1.898 g/cm3,C_9H_9N_3O_4Zn,Mr = 288.57,F(000) = 916,μ(MoKα) = 2.439 mm~(-1),Z = 4,R = 0.0600 and wR = 0.1306 for 2412 observed reflections(I 2σ(I)),and R = 0.0704 and wR = 0.1349 for all data. FJU-33 crystallizes in monoclinic space group P21/c with a = 12.7483(5),b = 9.9922(3),c = 9.8403(3) ?,β = 100.756(4)°,V = 1231.47(7) ?~3,Dc = 1.816 g/cm~3,C_(11)H_9N_7O_2Zn,Mr = 336.62,F(000) = 680,μ(Cu Kα) = 2.957 mm~(-1),Z = 4,R = 0.0478 and w R = 0.1184 for 2466 observed reflections(I 2σ(I)),and R = 0.0687 and w R = 0.1309 for all data. In FJU-32,Zn(Ⅱ) is coordinated to three μ3-OH groups forming an unprecedented 1D zigzag-like double chain,and the 1D double chains are connected to four neighbouring double chains by the cpt ligands to form an extended 3D porous coordination polymer. In FJU-33,the adjacent [Zn(atrz)] 2D layers are further connected by the cpt ligands via Zn–O coordinated bonds and neighboring interlayer hydrogen-bonding interactions to give rise to an overall 3D pillared layer structure. The neutron triazole group of the cpt ligand has weaker coordination ability than the triazolate anion of atrz ligand. Furthermore,FJU-32 and FJU-33 display high thermal stability up to 300 ℃,and the solid state fluorescence reveals that two new complexes are potential optical materials.     

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Polycarboxylate Ligand 5-(4-Hydroxypyridinium-1-ylmethyl)-isophthalic Acid: Synthesis,Structure, and Property

A Zn(Ⅱ) supramolecular coordination polymer, {[Zn_2(L)_2(m-bix)(H_2O)]·6 H_2O}n(1), with an interesting 1 D→2 D polythreading array from a flexible and angular organic aromatic polycarboxylate ligand 5-(4-hydroxypyridinium-1-ylmethyl)isophthalic acid(H2 L), and N-donor ligand 1,3-bis(imidazol-1-ylmethyl)benzene(m-bix), has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction(PXRD), IR, thermal gravimetric analyses(TGA) and single-crystal X-ray diffraction. In 1, the Zn(Ⅱ) center has two coordination geometries. One exhibits a trigonal bipyramidal coordination sphere, and the other is a tetrahedral geometry; L2-has two different coordination modes, with one connecting three Zn(Ⅱ) ions through two monodentate carboxylate groups and the monodentate hydroxyl group, and the other bridging two Zn(Ⅱ) ions through two carboxylate groups. The L2-anions connect the Zn(Ⅱ) centers forming an infinite 1 D tubular structure. These 1 D tubes are interconnected by the m-bix spacers to form a 2 D framework. Such 2 D layers are further assembled into a 3 D supramolecular network via hydrogen bonds. Meanwhile, the luminescent property of 1 has also been investigated in detail.     

Syntheses,Structures and Properties for Zn~Ⅱ Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2':6',3'-terpyridine Ligand

Two new Zn~Ⅱ coordination polymers,namely,[Zn L(o-bdc)]n(1) and [Zn L(mbdc)]_n·n H_2O(2)(L = 4?-(3-pyridyl)-3,2?:6?,3??-terpyridine,H_2(o-bdc) = benzene-1,2-dicarboxylic acid,H_2(m-bdc) = benzene-1,3-dicarboxylic acid),were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group,with a = 28.016(2),b = 11.3815(11),c = 19.8071(17) ?,β = 133.961(2)°,V = 4546.2(7) ?3,Z = 8,Mr = 539.83,Dc = 1.577 Mg/m~3,μ = 1.127 mm-1,F(000) = 2208,the final R = 0.0426 and w R = 0.0986 for 2875 observed reflections with I 2σ(I) and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group,with a = 15.6003(14),b = 11.9152(11),c = 26.633(3) ?,β = 94.320(2)°,V = 4936.5(8) ?~3,Z = 4,M_r = 1115.67,Dc = 1.496 Mg/m~3,μ = 1.043 mm~(-1),F(000) = 2272,the final R = 0.0499 and w R = 0.1342 for 2659 observed reflections with I 2σ(I) and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore,thermal stability and luminescent properties of 1 and 2 have also been investigated.     

A New 3d-4f Heterobimetallic Complex Based on 4,4?-Dicarboxybiphenyl Sulfone: Synthesis,Crystal Structure and Antifungal Activity

A new 3 d-4 f heterobimetallic complex [PrCu(sba)_2(Hsba)(H_2 O)_3]·H_2 O(1) based on a versatile ligand H_2 sba(H_2 sba = 4,4?-dicarboxybiphenyl sulfone) was prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Single-crystal X-ray diffraction indicates that complex 1 belongs to the monoclinic system, space group P2_1/n with a = 12.4642(11), b = 16.0586(16), c = 21.9678(19) ?, β = 92.888(1)o, V = 4391.4(7) ?~3, Z = 4, D_c = 1.800 g·cm~(-3), μ = 1.812 mm-1, M_r = 1190.31, F(000) = 2388, the final R = 0.0663 and wR = 0.1539 for 7737 observed reflections with I 2s(I). Complex 1 exhibits 2D network skeletons which are linked by hydrogen-bonding interactions to give a 3D supramolecular architecture. In addition, the antifungal effects of H_2 sba, metal salts and the title complex have also been studied by disc diffusion method against Colletotrichum gloeosporioides Penz. Complex 1 has better antifungal activity than H_2 sba and the corresponding metal salts. Complex 1 has potential applications in the antifungal activity.     

Organic Carboxylate Ligand Tuned Topological Variations in Three Zn(Ⅱ) Coordination Polymers: Syntheses,Crystal Structures and Photoluminescent Properties

Three new Zn(Ⅱ) coordination polymers, namely [Zn_2(suc)_2(bib)_2]_n·nH_2 O(1), [Zn(glu)(bib)]_n·4 nH_2 O(2), and [Zn(adp)(bib)]n(3)(bib = 1,4-bis(N-imidazolyl)butane, H_2 suc = succinic acid, H_2 glu = glutaric acid, H_2 adp = adipic acid) have been hydrothermally synthesized and structurally characterized. Compound 1 features a 3D framework with 4-connected hxg-d topological network, compound 2 is comprised of 2D 4~4-sql-type sheets, and the adjacent 2D sheets are further packed into a 3D supramolecular architecture via intermolecular hydrogenbonding interactions, and compound 3 is a 3D framework with 4-fold interpenetrating dia topology. The structural comparison of these three compounds demonstrates that the topological variations can be well controlled by employing aliphatic dicarboxylate ligands with different spacer lengths. Moreover, the thermal stabilities and photoluminescent properties of them were also studied in detail.     

Urothermal Synthesis and Crystal Structure of a Zn（Ⅱ） Coordination Polymer with a 3-D Supramolecular Structure

A new metal-organic coordination polymer [Zn(hfipbb)(e-urea)]n(1,H2hfipbb = 4,4'-(hexafluoroisopropylidene)bis(benzoic acid),e-urea = ethylene urea) has been urothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction.The title complex crystallizes in monoclinic,space group P21/c with a = 13.302(4),b = 10.981(3),c = 13.804(4) ,β = 93.587(5)°,V = 2012.3(10) 3,C20H14N2O5F6Zn,Mr = 541.72,Z = 4,Dc = 0.447 g/cm3, = 0.328 mm-1,F(000) = 272,R = 0.0340 and wR = 0.1107 for 4528 observed reflections(I >2σ(I)).In the structure of compound 1,two Zn(Ⅱ) ions are bridged by two carboxylate groups from two hfipbb ligands to form a dinuclear unit,and each dinuclear Zn(Ⅱ) unit is linked with its two adjacent dinuclear units through four hfipbb ligands into an infinite one-dimensional double-chain.The interesting structural feature of compound 1 is that the one-D double-chains are self-interconnected into a three-D supramolecular structure through hydrogen bonds between the coordinated e-urea molecules and carboxylate oxygen atoms(N1 and O2,N2 and O4).     

Synthesis, Structure and Geometrical Calculation of a Novel Co-crystal of {[4-Bromo-2-(benzimidazol-2-yl)phenolato][2- (1-butylbenzimidazol-2-yl)phenolato]zinc(Ⅱ)] and Bis[μ-2- (1- butylbenzimidazol-2-yl)phenolato]- 1κN3: 2κO; 1κO:2κN3-bis{[2-(1-butylbenzimidazol-2-yl)phenolato-κ2N3,O]zinc(Ⅱ)}

The title compound has been synthesized and characterized crystallographically. It is a co-crystal consisting of two different neutral zinc(Ⅱ) complexes with Hbpbm (Hbpbm = 4-bromo-2-(benzimidazol-2-yl)phenol) and Hnpbm (Hnpbm = 2-(1-butylbenzimidazol-2-yl)phenol).One is a monomeric mixed-ligand complex of [Zn(bpbm)(npbm)] 1 and the other a dimer of[Zn2(npbm)4] 2 with their ratio of 2:1. Thus the overall formula for the title compound is 21·2.Adjacent 1 and 2 are connected to each other by intermolecular hydrogen bonding interactions in the lattice. The crystal data: monoclinic, space group P21/c, a= 15.0141(12), b = 20.9941(17), c =18.4686(15) (A), β = 97.445(2)°, V= 5772.4(8) (A)3, Mr= 2429.68, Z = 2, Dc = 1.398 g/cm3,μ = 1.579mm-1, F(000) = 2504, R = 0.0637 and wR = 0.1771 for 6464 observed reflections (I＞ 2σ(Ⅰ)). The geometrical structure for 1 has also been theoretically optimized and compared with the experimental one.     

Two Metal Ion-controlled Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Based on 1,3,5-Benzenetricarboxylic Acid

Two new coordination polymers {[Zn(Hbtc)(bpyb)]·H_2O}n(1) and {[Cd(Hbtc)-(bpyb)_(1.5)]·0.5 bpyb}_n(2)(H_3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis(4-pyridyl)benzene) have been synthesized under hydrothermal conditions. The two compounds were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compound 1 displays a 2-fold interpenetrating 3D supramolecular architecture through O–H···N/O hydrogen bonds and π-π stacking interactions. Compound 2 exhibits a 2D→3D polycatenated structure, which is further stabilized by O–H···N hydrogen bonds. The results indicate that the metal ion has significant effects on the formation and structure of the resulted coordination polymers. Furthermore, thermal stability and photoluminescent properties of 1 and 2 are also discussed in detail.     

Synthesis and Characterization of a New 2D Ca(Ⅱ) Coordination Polymer Containing 1D Calcium-oxygen Chains

A new 2D Ca(Ⅱ) coordination polymer, [Ca(H2btc)(H2O)2]n(1, H4 btc = biphenyl-3,3',5,5'-tetracarboxylic acid), has been synthesized using the hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analysis, and photoluminescent analysis. Complex 1 crystallizes in the monoclinic system, space group C2/c with a = 17.5676(15), b = 11.4496(8), c = 7.6197(8)A, β = 102.787(2)o, V = 1494.6(2) A3, Z = 4, D3 c = 1.797 Mg·m-, μ = 0.483 mm-1, F(000) = 832, the final R = 0.0348 and wR = 0.0915 for 1521 observed reflections with I 2σ(I). Complex 1 has a 2D network containing 1D calcium-oxygen chains. These 2D networks are further connected by O–H···O hydrogen bonding interactions to generate a 3D supramolecular structure.     

A New Cd(Ⅱ) Coordination Polymer Constructed by 3-(2-Pyridyl)pyrazole and 5-Nitroisophthalic Acid:Synthesis,Crystal Structure and Theoretical Calculations

A new coordination polymer, [Cd_2(NIPH)(L)_2(H_2O)]n(1, HL = 3-(2-pyridyl)pyrazole and H_2NIPH = 5-nitroisophthalic acid), has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis, thermogravimetric analysis and fluorescence spectrum analysis. Complex 1 belongs to the triclinic system, space group P1 with a = 8.9539(6), b = 11.6252(8), c = 12.2472(8) ?, α = 80.011(2), β = 80.3850(10), γ = 86.773(2)°, V = 1237.37(14) ?~3, Z = 2, D_c = 1.987 g/cm~3, μ = 1.780 mm~(-1), M_r = 740.25, F(000) = 724, the final R = 0.0295 and wR = 0.1015 with I 2σ(I). Two H_2NIPH as monodentate and bidentate ligands and two L ligands link four Cd(Ⅱ) ions to form a tetranuclear subunit. Each pair of the tetranuclear subunits is bridged by NIPH ligands to yield a one-dimensional double-chain structure. Furthermore, the 1D chains are linked into a 3D supramolecular framework with hydrogen bonds and π-π interactions. In addition, we analyzed Natural Bond Orbital(NBO) in using the PBE0/LANL2DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Cd(Ⅱ) ion.     

A Novel Cd(Ⅱ)-MOF Constructed from an Organosillicon Tetracarboxylic Acid Ligand

A silicon-based tetracarboxylate connector has been prepared and employed in the construction of new metal-organic framework(MOF) material. A novel Cd(Ⅱ) coordination compound, namely, [Cd_4(H_2O)(L)(DMA)_2]_n(1, H_4L = 5,5?-(diphenylsilanediyl) diisophthalic acid, DMA = N,N-dimethylacetamide) has been successfully synthesized based on the ligand. X-ray single-crystal structure analysis reveals that polymer 1 crystallizes in monoclinic, space group P1 with a = 10.3335(11), b = 14.1557(15), c = 22.004(2) ?, α = 72.308(2), β = 88.105(2), γ = 88.363(3)o, V = 3064.2(6) ?~3, Cd_4Si_2C_(64)N_2O_(19)H_(52), Mr = 1659, Dc = 1.790 g/cm~3, μ(Mo Kα) = 1.486 mm~(-1), F(000) = 1630, Z = 2, the final R = 0.0660 and w R = 0.1302 for 12069 observed reflections(I 2σ(I)). Its structure has been further characterized by elemental analysis, thermogravimetric analyses and IR spectroscopy. Additionally, luminescent property of the title compound has been explored, and shows intense photoluminescent property in the solid state at room temperature.     

Hydrothermal Syntheses,Crystal Structures and Characteristics of Two New Isostructural Ni(Ⅱ) Coordination Polymers

Two new isostructure nickel(Ⅱ) coordination polymers, [Ni_2(5-Me-ip)(1,2-Bie)(H_2O)_2]_n(1) and [Ni2(5-Br-ip)(1,2-Bie)(H_2O)_2]n(2)(5-Me-H2 ip = 5-methylisophthalic acid, 5-Br-H2 ip = 5-mromoisophthalic acid, 1,2-Bie = 1,2-bis(imidazole)ethane), have been synthesized and structurally characterized by single-crystal X-ray diffraction. The result shows that complexes 1 and 2 crystallize in orthorhombic system, space group Pna21 with a = 16.3602(13), b = 10.1465(8), c = 21.8803(17) ?, V = 3632.1(5) ?3, Z = 4, D3 c = 1.525 g/cm, F(000) = 1728, R = 0.0292 and wR = 0.0668 for 6646 observed reflections(I 2σ(I)) for complex 1 and a = 16.409(3), b = 10.1625(17), c = 21.918(4) ?, V = 3654.9(11) ?3, Z = 4, Dc = 1.752 g/cm~3, F(000) = 1936, R = 0.0309 and wR = 0.0600 for 6809 observed reflections(I 2σ(I)) for complex 2. They both feature zigzag 2D layer structures, which are further staked along the a-axis through π···π and hydrogen interactions to form 3D supramolecular structures.