Polynuclear Silver(Ⅰ) Complexes with Phosphorus Ligands and 4,4'-Bipyridine:Synthesis,Structural Characterization and Spectroscopic Properties

Two novel silver(I) complexes {[Ag(OTf)(PPh3)(4,4'-bipy)]}∞(1) and {[Ag2-(OTf)2(dppb)3](CH3CN)4}∞(2)(OTf = trifluoromethanesulfonate, PPh3 = triphenylphophine, 4,4'-bipy = 4,4'-bipyridine, dppb = bis(diphenylphosphino)butane) have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Complex 1 crystallizes in orthorhombic, space group Pna21 with a = 19.259(2), b = 9.85070(12), c = 16.3827(17) ?, V = 3108.0(5) ?3, C29H23F3N2O3 PSAg, Mr = 675.39, Z = 4, Dc = 1.443 g/cm3, F(000) = 1360, μ = 0.816 mm-1, the final R = 0.0675 and w R = 0.1722 for 3662 observed reflections(I 2σ(I)). Complex 2 crystallizes in triclinic, space group P1 with a = 12.9370(11), b = 13.5261(13), c = 16.4539(15) ?, α = 106.7120(10), β = 97.3830(10), γ = 113.027(2)?, V = 2441.2(4)?3, C94H96F6N4O6P6S2Ag2, Mr = 1957.43, Z = 1, Dc = 1.331 g/cm3, F(000) = 1006, μ = 0.605 mm-1, the final R = 0.0717 and w R = 0.1795 for 5128 observed reflections(I 2σ(I)). Complex 1 is of zigzag chain structure, in which each Ag atom is coordinated by one OTf- anion, two N atoms from two 4,4'-bipy molecules and one P atom from PPh3 ligand. In 2, the central Ag atom is coordinated with one OTf- anion and three P atoms from three dppb ligands, which leads to the formation of a zigzag ring-bridge-ring chain with each ring consisting of two Ag atoms and two dppb ligands.     

Synthesis,Characterization and Luminescent Properties of Two Copper(Ⅰ) Complexes Based on 2,2?-Biquinoline and Phosphorous Ligand

Three new copper(Ⅰ) complexes, namely [Cu(DPEphos)(Biq)]CF_3SO_3(1) and [Cu(PPh_3)_2(Biq)]CF_3SO_3(2) and [Cu(PPh_3)_2(Biq)]ClO_4(3)(DPEphos = bis[2-(diphenylphosp hino)phenyl]ether, PPh_3 = triphenylphosphine and Biq = 2,2?-biquinoline), are synthesized and characterized by IR, ~1H NMR, ~(31) P NMR, fluorescence spectra and terahertz time-domain spectroscopy(THz-TDS). Complex 1 crystallizes in triclinic, space group P1 with a = 12.6997(5), b = 13.2813(5), c = 15.3593(6) ?, α = 80.211(3)°, β = 88.752(3)°, γ = 70.113(3)°, V = 2398.85(15) ?~3, C_(55)H_(41.2)CuF_3N_2O_(4.6)P_2S, Mr = 1018.27, Z = 2, Dc = 1.410 g/cm3, F(000) = 1048, μ = 0.628 mm-1, the final R = 0.0450 and w R = 0.1105 for 9419 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group C2/c with a = 19.9961(7), b = 15.9774(5), c = 17.7908(6) ?, β = 119.758(4)°, V = 4982.8(3) ?~3, C_(56.47)H_(47.88)CuF_3N_2O_(4.47)P_2S, Mr = 1040.54, Z = 4, Dc = 1.387 g/cm~3, F(000) = 2154, μ = 0.606 mm-1, the final R = 0.0430 and w R = 0.1218 for 4897 observed reflections(I 2σ(I)). Complex 3 crystallizes in monoclinic, space group C2/c with a = 19.7534(8), b = 15.0797(5), c = 17.8097(7) ?, β = 116.400(5)°, V = 4751.8(3) ?~3, C_(56)H_(45)ClCuN_3O_4P_2, Mr = 984.88, Z = 4, Dc = 1.377 g/cm~3, F(000) = 2040, μ = 0.635 mm-1, the final R = 0.0731 and w R = 0.2180 for 4670 observed reflections(I 2σ(I)). In the emission spectra, shifts of emission peak are derived from ligand-centered(π-π*) transition.     

Two Three-dimensional Supramolecular Polymer Built from Mixed N-Donor and Carboxylate Ligands

Two new complexes, [Mn(L)(mmbda)(H_2O)](1) and [Co(L)(btc)(H_2O)]·H_2O(2), were synthesized by reacting the corresponding metal(Ⅱ) salts with rigid ligand 1,4-di(1Himidazol-4-yl)benzene(L) and two different carboxylic acids of 5-methylisophthalic acid(H_2mmbda) and 1,2,4-benzenetricarboxylic acid(H_3btc), respectively. The structures of the complexes were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in triclinic, space group P1 with a = 6.9436(4), b = 9.7306(6), c = 15.5302(10) ?, α = 73.7430(10), β = 85.1010(10), γ = 70.0360(10)o, V = 946.75(10) ?~3, Z = 2, C_(21)H_(20)N_4O_5 Mn, M_r = 463.33, D_c = 1.618 g/cm~3, μ = 0.742-1, S = 1.002, F(000) = 474, the final R = 0.0285 and wR = 0.0600 for 4328 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group P2_1/n with a = 12.5216(12), b = 7.3312(8), c = 22.510(2) ?, β = 93.104(2)o, V = 2063.3(4) ?~3, Z = 4, C_(21)H_(18)N_4O_8Co, M_r = 513.31, D_c = 1.646 g/cm~3, μ = 0.892~(-1) mm, S = 1.096, F(000) = 1044, the final R = 0.0673 and wR = 0.1780 for 3594 observed reflections(I 2σ(I)). Both of complexes are one-dimensional(1D) chain structures and rich hydrogen bonds extend such 1D chains to form three-dimensional(3D) supramolecular polymers.     

Syntheses, Crystal Structures and Magnetism of Two New Coordination Polymers [Ni（bix）2Cl2]n and [Co（bix）Cl2]n

The self-assembly reactions of MIICl2 (M = Ni, Co) with the flexible bix ligand [bix = 1,4-bis(imidazole-1-ylmethyl)benzene] yielded a 2D network [NiII(bix)2Cl2]n 1 and a 1D chain [CoII(bix)Cl2]n 2. Their crystal structures have been determined by X-ray single-crystal diffraction analysis. Complex 1 characters a two-dimensional grid-type structure and crystallizes in monoclinic, space group P21/c with a = 7.7231(7), b = 12.7787(9), c = 13.9374(13) , β = 105.419(4)o, C28H28Cl2N8Ni, Mr = 606.19, Ζ = 2, V = 1326.0(2) 3, Dc = 1.518 g/cm3, μ = 0.969 mm-1, F(000) = 628, R = 0.0429 and wR = 0.0783 for 2503 observed reflections (I > 2σ(I)). Compound 2 is a one-dimensional chain and crystallizes in orthorhombic, space group Pbca with a = 11.3696(6), b = 10.2128(6), c = 14.4943(9) , C14H14Cl2CoN4, Mr = 368.12, Z = 4, V = 1683.01(17) 3, Dc = 1.453 g/cm3, μ = 1.334 mm-1, F(000) = 748, R = 0.0317 and wR = 0.0800 for 1778 observed reflections (I > 2σ(I)). Magnetic properties of the title complexes were also investigated.     

Synthesis and Optical Property of a New Zinc Complex Based on the Derivative of 2-(2'-Hydroxyphenyl)-1H-benzimidazole and Phenanthroline

A novel zinc complex(Zn E) has been designed and synthesized based on the derivative of 2-(2'-hydroxyphenyl)-1-H-benzimidazole(HBI) and the neutral nitrogen-containing ligand(phen). The crystal of the title complex crystallizes in the monoclinic system, space group P21/n with a = 10.2631(2), b = 34.2166(6), c = 11.4103(3) ?, β = 96.771(2)°, Mr = 844.24, V = 3978.99(14) ?3, Z = 4, the final R = 0.0400 and wR = 0.1001 for 8107 observed reflections(I 2σ(I)). In the title complex, the free protonated phenoxide moiety(4-OH) is successfully retained to realize pseudo-intramolecular hydrogen bonds with the coordinated O atom from the other ligand.     

Synthesis,Structural Characterization and Catalytic Activity of Copper(Ⅰ) Complexes with Triphenylphosphine and Pyridine Derivatives

Two new Cu(Ⅰ) complexes [CuCl(3-PyOH)(PPh_3)_2](1) and [Cu_2(μ-Cl)_2(4-Stpy)(Ph_3P)_3](2)(PyOH = hydroxypyridine; stpy = styrylpyridine) with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/c with a = 9.8945(7), b = 37.266(2), c = 10.9461(7) ?, β = 116.0750(10)°, V = 3625.3(4) ?~3, Z = 4, D_c = 1.350 Mg/cm~(-3), μ = 0.801 mm~(-1), F(000) = 1528, the final R = 0.0320 and w R = 0.0729 for 18568 observed reflections(I 2σ(I)), R(all data) = 0.0413, wR(all data) = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2_1/c with a = 11.290(3), b = 20.388(5), c = 24.092(6) ?, β = 102.028(4)°, V = 5424(2) ?~3, Z = 4, D_c = 1.428 Mg/cm~(-3), μ = 1.016 mm~(-1), F(000) = 2408, the final R = 0.0568 and w R = 0.1486 for 27644 observed reflections(I 2σ(I)), R(all data) = 0.0716, wR(all data) = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu(I) complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.     

Syntheses,Crystal Structures,and Properties of Two New Lanthanide Coordination Polymers Constructed from Benzimidazole-5,6-dicarboxylic Acid

Two lanthanide coordination polymers, {[Ln(Hbidc)(bidc)(H2 O)3]·3 H2 O}n(H3 bidc = benzimidazole-5,6-dicarboxylic acid, Ln = Eu(1), Sm(2)) have been hydrothermally synthesized. Both compounds are isostructure and crystallize in the P2_1/c space group of monoclinic system. Complex 1: a = 11.087(6), b = 8.972(5), c = 23.064(13) ?, b = 95.027(5)o, V = 2285.4(2) ?~3, Z = 4, Mr = 669.35, Dc = 1.945 g/cm~3, F(000) = 1328, S = 1.044, μ = 2.827 mm~(-1), R = 0.0393 and wR = 0.0801 for 3458 observed reflections(I 2s(I)). Complex 2: a = 11.087(6), b = 8.972(5), c = 23.064(13) ?, b = 95.027(5)°, V = 2285.4(2) ?~3, Z = 4, Mr = 667.74, Dc = 1.941 g/cm~3, F(000) = 1324, S = 1.071, μ = 2.652 mm~(-1), R = 0.0329 and wR = 0.0809 for 3744 observed reflections(I 2s(I)). Complexes 1 and 2 have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and thermogravimetric analyses(TGA). The single-crystal X-ray diffraction analysis reveals that complexes 1 and 2 are the isostructural 1 D zigzag chain structures, which are further extended into a 3 D supramolecular structure through hydrogen bonds and p···p stacking interactions. Furthermore, the thermal stability, UV-vis absorption spectra and fluorescent properties of complexes 1 and 2 have been investigated and discussed in detail.     

One-dimensional Coordination Polymers Assembled into Two Supramolecular Frameworks with High Stability

The dual ligand system of V-shaped 5-(4-carboxy-2-nitrophenoxy)-isophthalic acid(Hcn-H2ipa) and dipyridy-type molecules produces two new coordination polymers: {[Ni(cn-Hipa)(bpa)(H2O)3]·1.5H2O}n 1 and {[Cu(Hcn-ipa)(ppe)2]}n 2(bpa = 1,2-bis(4-pyridyl)ethane, and ppe = trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene). Two complexes have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, and thermogravimetric analysis(TGA). Complex 1 is of monoclinic system, space group C2 with a = 25.936(3), b = 7.6100(10), c = 16.558(2), β = 105.9470(10)°, V = 3142.4(7) ?3, Dc = 1.415 g/cm3, Mr = 669.23, Z = 4, F(000) = 1388, μ = 0.687 mm-1, the final R = 0.0397 and w R = 0.0967 for 12070 observed reflections with I 2σ(I). Complex 2 belongs to the triclinic system, space group P1 with a = 10.165(5), b = 14.946(7), c = 15.506(11) ?, α = 106.461(7), β = 102.454(8), γ = 107.861(5)°, V = 2029(2) ?3, Dc = 1.266 g/cm3, Mr = 773.20, Z = 2, F(000) = 794, μ = 0.595 mm-1, the final R = 0.0538 and w R = 0.1378 for 15488 observed reflections with I 2σ(I). Two complexes show that the 1D polymeric chains are cohered together by extensive H-bonds to complete stable supramolecular microporous frameworks.     

A Novel Zn(Ⅱ) Complex with 4-Connected umc Topology:Synthesis,Crystal Structure and Luminescent Property

A novel complex, [Zn(L)]2·H2O(1, H2 L = 4-aminophthalic acid), has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group C2/c with a = 12.4267(6), b = 7.7482(3), c = 18.6983(8) ?, β = 110.437(3)o, V = 1687.04(13) ?3, Z = 4, C16H12N2O9Zn2, Mr = 507.06, Dc = 1.996 g/cm3, μ = 2.903 mm-1, S = 0.989, F(000) = 1016, the final R = 0.0304 and w R = 0.0720 for 12618 observed reflections(I 2σ(I)). Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional(3D) framework with 4-connected umc topology. Moreover, the thermogravimetric(TG) analysis and photoluminescent property of 1 were also discussed.     

Structure and Luminescence of Carboxylic Acid Samarium and Europium Complexes

Two crystals, [Sm(Hcpna)(cpna)·3 H_2O]n(1) and [Eu(Hcpna)(cpna)·2 H_2O]n(2),have been synthesized by solvothermal method based on Sm3+ and Eu3+ with multiple acid ligands5-(4-carboxyphenoxy)nicotinic acid(H_2cpna), and the new complexes have been characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis and fluorescence analysis. Complex 1 exhibits a 1 D chain structure. It crystallizes in the triclinic system, space group P1 with a = 5.9738(11), b = 12.528(2), c = 18.021(4) ?, α = 93.156(3)o, β =98.067(3)o, γ = 92.692(3)o, V = 1331.3(4) ?3, Z = 2, S = 1.069, F(000) = 702, R = 0.0277 and wR =0.0688(I 2σ(I)). Complex 2 shows a two-dimensional network structure, which crystallizes in monoclinic system, space group C2/c with a = 13.6733(19), b = 18.422(3), c = 10.4307(15) ?, β =93.881(2)o, V= 2621.4(7) ?3, Z = 4, S = 1.110, F(000) = 1372, R = 0.0302 and wR = 0.0811(I 2σ(I)). The solid-state fluorescent test results show tcomplex 1 has weaker fluorescence intensity than the ligand. However, complex 2 has excellent fluorescence properties, and can emit bright red light under the irradiation of ultraviolet lamp.     

Syntheses and Crystal Structures of Two Isomeric Au Complexes

<正>Two new isomeric Au complexes,Au(PPh_3)(bmt),have been synthesized via the reaction of Au(PPh_3)Cl with 2-benzimidazolethiol(Hbmt)in dichloromethane(CH_2Cl_2)solution. Their crystal structures were determined by elemental analysis and single-crystal X-ray diffraction studies.Complex 1 crystallizes in the monoclinic system,space group C2/c with a=19.589(2),b= 21.1368(15),c=23.424(2)(?),β=108.346(4)°,V=9206.1(14)(?)~3,M_r=1216.85,D_c=1.756 g/cm~3,μ=6.566 mm~(-1),F(000)=4704,Z=8,the final R=0.0563 and wR=0.1028 for 8125 reflections with I2σ(I).Complex 2 crystallizes in the monoclinic system,space group P2_l/n with a= 9.627(3),b=21.384(8),c=22.308(8)(?),P=92.068(6)°,V=4590(3)(?)~3,M_r=1216.85,D_c=1.761 g/cm~3,μ=6.585 mm~(-1),F(000)=2352,Z=4,the final R=0.0500 and wR=0.0883 for 10477 reflections with I2σ(I).X-ray diffraction studies reveal that complexes 1 and 2 both feature a 1D chain along the a axis.     

Synthesis and Characterization of Three Vanadium（Ⅴ） Complexes Incorporating Tridentate Hydrazone Ligands of Thiophene-2-carboxylic Hydrazide and 2-Furoic Acid Hydrazide

Divanadium(Ⅴ) complex [VO(aptch)(μ-OCH3)]2(1) and two monovanadium(Ⅴ) complexes [VO(apfah))(OEt)](2a and 2b,H2aptch = 2-hydroxyacetophenone thiophene-2-car-boxylic hydrazone,H2apfah = 2-hydroxyacetophenone 2-furoic acid hydrazone) have been synthesized and characterized.Single-crystal X-ray diffraction studies reveal that 1 is a cen-trosymmetric dimer bridged by two methoxido O-atoms.Complex 1 crystallizes in the monoclinic crystal system,space groups P21/c with a = 7.4825(4),b = 17.0928(11),c = 11.6961(7) ,β = 98.172(4)o,Z = 2,F(000) = 728,μ = 0.829 mm-1,the final R = 0.0457 and wR = 0.1137 for 2654 observed reflections with I > 2(I).The vanadium(V) is coordinated to the tridentate ligand,ethanol molecule to form a distorted square-pyramidal geometry,complexes 2a and 2b.Although 2a and 2b have the same asymmetric unit,they belong to different space groups.Complex 2a crystallizes in the monoclinic crystal system,space groups P21/n with a = 10.2293(2),b = 15.6660(3),c = 10.6298(2) ,β = 116.259(1)o,Z = 4,μ = 0.676 mm-1;complex 2b crystallizes in the triclinic crystal system,space groups P with a = 8.2808(4),b = 9.4704(5),c = 10.0819(5) ,α = 86.133(3),= 81.956(3),γ = 80.248(3)o,Z = 2 and μ = 0.670 mm-1.The hydrogen bonds are found to exist in 2b only.The crystal structure is stabilized by intermolecular hydrogen bonds of C-H···O.     

Coordination Modes of Polypyridyl Quinoxaline with Hg(Ⅱ),Pb(Ⅱ),Co(Ⅱ) and Mn(Ⅱ)

The interaction of metal ions(Hg~(2+),Pb~(2+),Co~(2+),Mn~(2+)) with polypyridyl quinoxaline ligand 2,3,6,7,10,ll-hexakis(2-pyridyl)dipyrazino[2,3-f:20,30-h]quinoxaline(HPDQ) was investigated,and four new complexes have been synthesized and characterized.Complex 1 exhibits a 0dimensional dual-core structure,2 is a one-dimensional chain structure based on a dual-core Pb unit,while 3 and 4 show a 0 dimensional single-core structural unit.Complex 1 is of monoclinic system,space group C2/c with a = 19.211(4),b = 23.896(5),c = 12.698(3) ?,β= 120.11(3)°,V= 5043.0(17)?~3,Z = 4,S = 1.053,F(000) = 2976,R~a = 0.0637 and wR~b = 0.1068(I 2σ(I)).Complex 2 adopts triclinic system,space group P1 with a = 10.370(2),b = 12.195(2),c = 21.033(4) ?,α = 80.87(3),β= 81.22(3),γ = 82.38(3)°,V= 2579.3(8) ?~3,Z = 2,S = 1.099,F(000) = 1328,R~a = 0.0609 and wR~b =0.1365(I 2σ(I)).Complex 3 is of monoclinic system,space group Cllc with a = 14.166(3),b =16.621(3),c = 20.248(4) ?,β = 92.18(3)°,V= 4764.0(16) ?~3,Z = 4,S = 1.005,F(000) = 2108,R~a =0.0589 and wR~b = 0.1332(I 2σ(I)).Complex 4 belongs to the monoclinic system,space group C2/c with a = 14.404(3),b = 16.626(3),c = 20.346(4) ?,β = 92.43(3)°,V= 4868.2(17) ?~3,Z = 4,S= 1.068,F(000) = 2108,R~a = 0.0833 and wR~b = 0.1591(I 2σ(I)).Furthermore,the behavior of HPDQ with Hg~(2+),Pb~(2+),Co~(2+) and Mn~(2+) in the solution was also investigated,and the result shows after the metal ions were added respectively,the emission of all solutions shows fluorescence quenching and has a red shift compared with that of the HPDQ ligand.     

CRYSTAL STRUCTURE OF Pt（dppe）（SPh）2

<正> Anaerobic reaction of Pt (dppe)Cl2 (dppe = Ph2PCH2CH2PPh2) with NaSPh and elemental selenium affords complex Pt(dppe)(SPh)2,which crystallizes in the monoclinic system space group C2/c with a=14. 392(7) ,b=16. 380(7) ,c=14. 266(5) A ,β=86. 44(4)°,V=3342(5) A3,Z = 4,Dc=1. 613g/cm3,and μ(MoKa) = 44. 813 cm-1. The final structural refinement converged with unweighted and weighted R factors of 0. 041 and 0. 057 for 2206 observed reflections (I>3σ(I)). X-ray analysis shows that the Pt atom in Pt(dppe)(SPh)2 is at the center of the approximately planar tetragon of two P atoms and two S atoms.     

Crystal Structure and Spectroscopic Analysis of Polypyridyl Quinoxaline with Ce(Ⅲ) and Nd(Ⅲ)

Two high coordination crystals were obtained by the interaction of Ce~(3+) and Nd~(3+) with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis(2-pyridyl)dipyrazino[2,3-f:20,30-h]quinoxaline(HPDQ), and they were characterized. Complex 1 exhibits a 0 dimensional three-nuclear structure, with the three Ce(Ⅲ) atoms being ten-, eleven- and twelve-coordinated. Complex 2 is a 0 dimensional dual-core structure and the Nd(Ⅲ) atom is ten-coordinated. Complex 1 is of monoclinic system, space group P2/c with a = 16.850(3), b = 16.617(3), c = 24.017(5) ?, β = 100.94(3)o, V = 6602(2) ?~3, Z = 4, S = 1.062, F(000) = 3372, R = 0.0504 and wR = 0.1463(I 2σ(I)). Complex 2 adopts a monoclinic system, space group C2/c with a = 25.795(5), b = 20.166(4), c = 13.059(3) ?, β = 112.29(3)°, V = 6286(2) ?~3, Z = 4, S = 1.004, F(000) = 2664, R = 0.0663 and wR = 0.1821(I 2σ(I)). Furthermore, the behaviors of HPDQ with Ce~(3+) and Nd~(3+) in the solution are also investigated. After the Ce~(3+) is added, the ultraviolet absorption of the solution is enhanced with a red shift compared with that of the HPDQ ligand. While after adding Nd~(3+), the ultraviolet absorption of the solution is weakened, and it has a red shift which is the same as Ce~(3+). However, after the respective addition of metal ions, the emission of all solutions is quenched and has a red shift compared with that of the HPDQ ligand.     

Crystal Structure and the Third-order Nonlinear Optical Property of a Cadmium(Ⅱ) Complex Based on a D-π-A Structural Organic Ligand

A triphenylamine-containing Schiff base ligand(L), namely, N-(4-(1 H-imidazol-1-yl)benzylidene)-N,N-diphenylbenzene-1,4-diamine, was synthesized and characterized. By coordination of the ligand with CdI2, a complex CdI2 L2 was obtained. The structure of the complex was analyzed through single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 25.277(5), b = 11.176(5), c = 17.912(5) ?, β = 106.056(5)°, V = 4863(3) ?3, Z = 4, Dc =1.633 Mg/m3, F(000) = 2360, Μr = 1195.19, μ = 1.766 mm-1, the final R = 0.0323 and wR = 0.0758 for 33414 observed reflections with I 2?(I). The linear absorption spectra of the complex were experimentally and theoretically studied. And the third-order nonlinear optical(NLO) property of the complex was also measured through Z-scan technique.     

Syntheses,Crystal Structures and Antibacterial Activities of Cobalt(Ⅱ) and Manganese(Ⅱ) Complexes with Schiff Base Ligand Derived from Tryptamine

Two new mononuclear complexes, namely [Co(L)_2](1) and [Mn(L)_2](2)(HL = N-(3-methylsalicylidene)tryptamine), have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in anhydrous ethanol. The crystal structures of the complexes were characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group C2/c, with a = 23.146(2), b = 9.4864(10), c = 13.9261(15) ?, β = 102.898(2)°, V = 2980.6(5) ?3, Z = 4, Dc = 1.367 g/cm3, F(000) = 1284 and μ = 0.616 mm-1. Complex 2 crystallizes in monoclinic, space group P21/n, with a = 14.807(11), b = 13.118(10), c = 16.663(13) ?, β = 111.237(14)°, V = 3017(4) ?3, Z = 4, Dc = 1.342 g/cm~3, F(000) = 1276 and μ = 0.477 mm-1. The units of complex 1 are linked by intermolecular N–H···π hydrogen bonds into infinite 1D chains, which are further extended into a 3D supramolecular structure by a series of π···π stacking interactions. The units of complex 2 are linked by intermolecular N–H···π hydrogen bonds and C–H···π hydrogen bonds into an infinite 3D supramolecular structure. Meanwhile, the antibacterial activities of the ligand and its complexes have been tested against four kinds of bacteria. The results show that the three compounds all have excellent antibacterial activities and that 1 and 2 possess stronger inhibiting effects against the bacteria than the Schiff base.     

Synthesis,Structure and Photocatalytic Activity of Two 4-(2,6-Di(pyrazin-2-yl)pyridin-4-yl)benzoate-Based Chain Complexes

Two new one-dimensional chains extended by alternate benzenedicarboxylate(BDC) and 4-(2,6-di(pyrazin-2-yl)pyridin-4-yl)benzoate(L~-) connectors, {[Cu(L)(BDC)_(0.5)]·3.5 H_2 O}_n (1) and {[Zn(L)(BDC)_(0.5)] ·H_2 O}_n (2), were solvothermally synthesized. Complex 1 is in triclinic system, space group P1 with a = 9.6456(14), b = 11.1160(16), c = 12.0414(18) ?, α = 106.266(3), β = 92.277(3), γ =108.104(3)°, V = 1166.6(3) ?~3, D_c = 1.603 g·cm~(-3), Mr = 563.00, Z = 2, F(000) = 578, μ = 0.996 mm~(-1), the final R = 0.0575 and wR = 0.1386 for 3704 observed reflections with I 2σ(I). Complex 2 crystallizes in monoclinic, space group C2/c with a = 28.607(5), b = 8.9767(16), c = 19.705(4) ?, β = 125.396(3)°, V = 4125.0(13) ?~3, D_c = 1.674 g·cm~(-3), Mr = 519.79, Z = 8, F(000) = 2120, μ = 1.242 mm~(-1), the final R = 0.0487 and w R = 0.0907 for 2944 observed reflections with I 2σ(I). Resulting from the narrower band gap and broader response to visible light, the CuII-chain exhibits better photocatalytic performance towards the degradation of rhodamine B and methylene blue than those of ZnII-chain.     

A New Three-dimensional Supramolecular Polymer Built from Non-covalent Bonding Interactions

A new complex, [Ni2(L)4(H2O)8](1, L1 = 4-(1H-imidazol-4-yl)benzoic acid), has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c with a = 22.281(2), b = 7.3959(7), c = 24.978(3) ?, β = 90.876(10), V = 4115.6(7) ?3, Z = 8, C20H22N4O8Ni, Mr = 505.13, Dc = 1.630 g/cm3, μ = 1.001 mm-1, S = 1.080, F(000) = 2096, the final R = 0.452 and wR = 0.1152 for 9380 observed reflections(I 2σ(I)). The result of X-ray diffraction analysis revealed three different kinds of Ni(II) centre mononuclear molecules in the asymmetric unit. The independent mononuclear units are bridged to form a three-dimensional supramolecular polymer by extensive hydrogen bonds and C–H···π non-covalent bonding interactions.     

Synthesis,Crystal Structure and Catalytic Activity of a Pd-PEPPSI Complex Bearing Bromine Group

A new Pd-PEPPSI complex(2) with the bromo groups on the para-positions of N-aryl moieties of NHC has been synthesized and characterized by NMR and X-ray single-crystal diffraction. Complex 2 crystallizes in monoclinic, space group P2_1/c with a = 11.8790(8), b = 14.3038(10), c = 15.9905(11) ?, β = 101.291(2)°, V = 2664.4(3) ?3, Z = 4, D_c = 1.722 Mg/m~3, μ = 3.913 mm~(-1), F(000) = 1352, the final R = 0.0682 and wR = 0.1914 for 15113 observed reflections(I 2σ(I)), R(all data) = 0.0970, w R(all data) = 0.2115, completeness to theta of 25.00 is 100.0% and GOOF = 1.035. Influenced by the electron-withdrawing bromo groups, the Pd-PEPPSI complex(2) showed high catalytic activity for the Suzuki-Miyaura cross-coupling reactions of aryl chlorides and arylboronic acids with a low catalyst loading(0.05 mol%) at room temperature in air.