Two new coordination polymers,named {[Co3（pfca）6（phen）2]·2H2O}n（1） and[Cu（pfca）2（4,4＇-bpy）（H2O）]n（2）（Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine）,were hydrothermally synthesized an...Two new coordination polymers,named {[Co3（pfca）6（phen）2]·2H2O}n（1） and[Cu（pfca）2（4,4＇-bpy）（H2O）]n（2）（Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine）,were hydrothermally synthesized and characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 crystallizes in the triclinic crystal system,space group P1 with a = 10.939（3）,b = 12.430（4）,c = 13.815（4） A,α=78.436（3）,β= 70.261（3）,γ= 80.268（3）°,V= 1721.8（9） A^3,Dc = 1.508 g/cm^3,Mr= 1564.06,Z = 1,F（000） = 799,μ= 0.802 mm^（-1）,the final R = 0.0432 and wR = 0.1015 for 13250 observed reflections with I 2σ（I）.Complex 2 is of monoclinic system,space group P2／lc with a =15.4985（14）,b = 15.8424（14）,c = 10.9528（10） A,β= 107.1600（10）°,V= 2569.6（4） A^3,Dc = 1.468g/cm^3,Mr = 568.02,Z = 4,F（000） = 1164,μ= 0.906 mm^（-1）,the final R = 0.0371 and wR = 0.0842 for 18183 observed reflections with I〉 2σ（I）.Complex 1 features linear Co（Ⅱ）-trinuclear units,which are assembled into a final 3D supramolecular structure through π…π stacking interactions and F-H weak interactions.Complex 2 consists of 1D polymeric Cu（Ⅱ）-chains that are further cohered together by extensive H-bonds.展开更多
A novel complex Mn3（2,2＇-bipy）ff3,5-DMBA）6 with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＇-bipyridine （2,2＇-bipy） has been synthesized by means of a solvent method. It crystallizes in the monoclinic space ...A novel complex Mn3（2,2＇-bipy）ff3,5-DMBA）6 with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＇-bipyridine （2,2＇-bipy） has been synthesized by means of a solvent method. It crystallizes in the monoclinic space group C2/c with a = 3.1118（6）, b = 1.1754（2）, c = 2.0887（4） nm, β = 118.50（3）°, V= 6.714（2） nm3, Dc = 1.384 g/cm3, Z = 8, F（000） = 2912, the final GOOF = 1.078, R = 0.0691 and wR = 0.1455. The crystal structure shows that the three coordinated manganese（II） ions lie in a line with the middle one as the symmetric center. The distance between the central manganese（II） and the symmetric one is 0.3549 nm. There exist two coordination modes for the three manganese （II） ions： the symmetric manganese（II） ions are coordinated with three oxygen atoms and two nitrogen atoms from three 3,5-DMBA molecules and one 2,2＇-bipy molecule, respectively, forming a distorted square-pyramidal coordination geometry; the middle manganese（II） ion is coordinated with six oxygen atoms from six 3,5-DMBA molecules, generating a distorted octahedral coordination geometry. Spectrum properties of the complex were also studied.展开更多
A novel trinuclear nickel（II） complex [Ni3（bushz）z（Himdz）2（H20）2].2DMF （1, bushz = N-butylsalicylhydrazide, Himdz = imidazole, DMF = N,N-dimethyl-forrnamide） has been synthesized and characterized by X-ray s...A novel trinuclear nickel（II） complex [Ni3（bushz）z（Himdz）2（H20）2].2DMF （1, bushz = N-butylsalicylhydrazide, Himdz = imidazole, DMF = N,N-dimethyl-forrnamide） has been synthesized and characterized by X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P2 1/c with a = 7.706（7）, b = 14.882（6）, c = 18.639（6） A, β = 108.08（2）°, V= 2032（1） A3, Dc = 1.525 g/cm3, Mr = 932.95, Z= 2, F（000） = 972,μ = 1.442 mm-1, the final R = 0.0359 and wR = 0.0771. The three nickel（II） atoms in 1 are arranged in a strictly linear structure and exhibit alternating square-planar and octahedral geometries. The complex is connected to form a supramolecule with an infinite three-dimensional network through intermolecular hydrogen bonds. The electrochemical studies reveal that redox of Ni3＋/Ni2＋ in the complex is a quasi-reversible process. The thermal stability of the title complex was also studied.展开更多
A Schiff base ligand（H2CSF,C13H11NO4,1） derived from 3-carboxylsalicylaldehyde and furfurylamine,and its trinuclear complex [Ni3（CSF）2（CH3COO）2（DMF）2（H2O）2]（2） were synthesized.Compound 1 was characterized...A Schiff base ligand（H2CSF,C13H11NO4,1） derived from 3-carboxylsalicylaldehyde and furfurylamine,and its trinuclear complex [Ni3（CSF）2（CH3COO）2（DMF）2（H2O）2]（2） were synthesized.Compound 1 was characterized by elemental analysis,1H NMR,IR,MS and X-ray diffraction analysis.The crystal of 1 belongs to the monoclinic system,space group P21/c with a = 8.472（2）,b = 19.743（5）,c = 7.2300（18） ,β = 110.278（4）°,V = 1134.4（5） 3,Z = 4,Mr = 245.23,Dc = 1.436 g·cm-3,μ = 0.108 mm-1,F（000） = 512,λ = 0.71073 ,the final R = 0.0440 and wR = 0.1199 for 1426 observed reflections（I 2σ（I））.In the crystal of 1,there exist intramolecular hydrogen bonds and weak intermolecular C-H···O hydrogen bonds.Compound 2 was characterized by elemental analysis,IR,TG and X-ray diffraction analysis.The crystal of 2 is of triclinic system,space group P1 with a = 10.1237（17）,b = 10.4086（18）,c = 10.4884（18） ,α = 82.528（2）,β = 67.339（2）,γ = 83.010（2）°,V = 1008.1（3） 3,Z = 1,Mr = 962.87,Dc = 1.586 g·cm-3,μ = 1.463 mm-1,F（000） = 498,λ = 0.71073 ,the final R = 0.0517 and wR = 0.0805 for 2065 observed reflections（I 2σ（I））.The geometry of the trinuclear molecule is centrosymmetric,in which every Ni（Ⅱ） ion is coordinated in a slightly distorted octahedron.The three Ni（Ⅱ） ions are arranged in a straight line.The two CSF2-ions act as NOO tridentate ligands with the phenolate and carboxylate oxygen as bridging atoms.The coordination atoms of CSF2-anions and water molecules are coordinated on the equatorial plane,while the two bridging acetate ions and two DMF are trans-coordinated on the apical sites.展开更多
The coordination polymer, [Mn3（bpta）2（bip）2], （H3bpta = biphenyl-3,3＇,5-tricar- boxylic acid, bip = 2,6-bis（imidazole-1-yl）pyridine）, has been synthesized under hydrothermal con- ditions and characterized by ...The coordination polymer, [Mn3（bpta）2（bip）2], （H3bpta = biphenyl-3,3＇,5-tricar- boxylic acid, bip = 2,6-bis（imidazole-1-yl）pyridine）, has been synthesized under hydrothermal con- ditions and characterized by elemental analysis, FT-IR, XRD, TGA and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.919（3）, b = 9.780（2）, c = 20.352（7） A, V = 2344.4（10） A3, Z= 2, C52H32Mn3N10012, Mr = 1153.70, Dc = 1.634 g/cm3, p（MoKa） = 0.876 mm-1, F（000） = 1170, the finalR = 0.0605 and wR = 0.1177. The complex forms a 2D layer with trinuclear Mn（II） units and further assembles into a 3D supramolecular network structure through C-H..＇O hydrogen bonding and C-H...π interactions. Moreover, the negative J value indicates the presence of antiferromagnetic coupling between the Mn（II） ions within a trinuclear unit.展开更多
A three-dimensional framework copper（Ⅱ） coordination polymer with copper carbonate basic and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） has been hydrothemally synthesized.The complex （2,C14 H10 CuN8 ·3H2 O） c...A three-dimensional framework copper（Ⅱ） coordination polymer with copper carbonate basic and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） has been hydrothemally synthesized.The complex （2,C14 H10 CuN8 ·3H2 O） crystallizes in tetragonal,space group P4 2 /n,a=2.08581（12）,b=2.08581（12）,c=0.72331（4） nm,M r=761.73,V=3.1468（3） nm 3,Dc=1.608 g/cm 3,Z=4,F（000）=1552,GOOF=1.07,R=0.0515 and wR=0.1689.Every asymmetric unit molecular structure of the complex is composed with one copper ion,one and half water molecules and two Hpt molecules.Each copper ion is coordinated with five nitrogen atoms from four Hpt molecules,forming a distorted square pyramidal geometry.The fluorescence spectrum analysis shows that the title complex at room temperature exhibits intense photoluminescence with maximum emission at 450 nm.The quantum chemistry calculation study on the complex has been performed.The stability,some frontier molecular orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.展开更多
In this paper detailed studies of the cyclic voltammetry(CV) of trinuclear metal cluster compounds [M_3O_2(O_2CCH_3,)6(H,O),j z+ (M,=Mo3,MoW2,W3) are reported.The result of CV shows that they are similar to each other...In this paper detailed studies of the cyclic voltammetry(CV) of trinuclear metal cluster compounds [M_3O_2(O_2CCH_3,)6(H,O),j z+ (M,=Mo3,MoW2,W3) are reported.The result of CV shows that they are similar to each other.There are a reversible redox peak near-0. 48 V and an irreversible reduced peak near-1.10 V in the scan range of + l.0 V to l. 5 V.It implies that the M_3O_2,clusters might gain one electron to be further reduced.But the two-electron-reduced product of M_3O_2 clusters are instable.The theoretical calculations(EHMO) agree well with the result of the CV experiment.展开更多
Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,...Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,10-phenanthroline, Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, and DMF = N,N-dimethylformamide） have been synthesized by using mononuclear [Fe（Phen）2（CN）2]·2H2O and [Fe（bpy）2（CN）2]·3H2O as precursors. These two complexes crystallize in monoclinic space groups P21/c and C2/c, respectively. For 1, a = 25.164（2）, b = 12.0405（11）, c = 20.4433（15） A, β = 91.948（3）°, V = 6190.5（9） A^3, Z = 4, Mr = 1418.90, Dc = 1.522 g/cm^3, F（000） = 2936, μ = 1.161 mm^-1, the final R = 0.0722 and wR = 0.2011 for 10779 observed reflections （I 〉 2σ（I））. For 2, a = 43.5945（0）, b = 11.8447（0）, c = 29.5637（2）A, β = 120.430（11）o, V = 13162.76（9） A^3, Z = 8, Mr = 1518.48, Dc = 1.533 g/cm^3, F（000） = 6288, μ = 1.101 mm^-1, the final R = 0.0711 and wR = 0.1783 for 11262 observed reflections （I 〉 2σ（I））.展开更多
Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and full...Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu（Ⅱ）and Zn（Ⅱ）] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate（HPNP）.The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.展开更多
The coordination polymer,[Mn3（L） 2（adip） 3]·2H2O（L = 2-（4-fluorophenyl） -1H-imidazo[4,5-f] [1,10]phenanthroline and H2adip = adipic acid） ,has been synthesized under hydro-thermal conditions and character...The coordination polymer,[Mn3（L） 2（adip） 3]·2H2O（L = 2-（4-fluorophenyl） -1H-imidazo[4,5-f] [1,10]phenanthroline and H2adip = adipic acid） ,has been synthesized under hydro-thermal conditions and characterized by elemental analysis,IR and single-crystal X-ray diffraction. It crystallizes in triclinic,space group P1^- with a = 8.4085（11） ,b = 11.1273（14） ,c = 14.5758（18） ,α = 78.528（2） ,β = 75.425（2） ,γ = 78.143（2） °,V = 1276.0（3） A^3,Z = 1,C56H50F2Mn3N8O14,Mr = 1261.86,Dc = 1.642 g/cm^3,F（000） = 647,μ（MoKa） = 0.819 mm^-1,R = 0.0446 and wR = 0.1008. The backbones of the two types of adip dianions link the neighboring trinuclear Mn（Ⅱ） clusters to yield a two-dimensional layer structure. The large conjugated L ligands are located on both sides of the two-dimensional layers. Additionally,the O-H···O,O-H···N and N-H···O hydrogen bonds further stabilize the structure.展开更多
A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and wat...A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and water. It crystallizes in the monoclinic space group C2/c with a = 31.1497（15）, b = 11.7576（6）, c = 20.9049（10） A, fl = 118.4550（10）°, V- 6731.4（6） A3, Dc = 1.412 g/cm3, Z = 4, F（000） = 2972, GOOF = 1.069, the final R= 0.0667 and wR= 0.1917. The whole molecule consists of three zinc ions, six 3,5-DMBA molecules, two 2,2＂-bipyridine molecules and one and half water molecules, in which three zinc ions are bridged by six μ2-η1：η0 carboxylate groups of 3,5-DMBA. The Zn（1） atom is centrosymmetric, and adopts a distorted octahedral ZnO6 geometry, while the Zn（2） gives a distorted square pyramidal ZnOsN2 geometry. The spectroscopic characterization and thermal stability properties of the complex were investigated.展开更多
By the reaction of bidentate ligand 1,1'-bis(diphenylphosphino)-ferrocene (dppf) with MoCl_4(CH_3CN)_2, a novel bonding type complex (MoCl_4)2_· (dppf) was synthesized and characterized by elemental analyses,...By the reaction of bidentate ligand 1,1'-bis(diphenylphosphino)-ferrocene (dppf) with MoCl_4(CH_3CN)_2, a novel bonding type complex (MoCl_4)2_· (dppf) was synthesized and characterized by elemental analyses, ^(31)p-NMR, IR and electronic spectra, TG and ICP-AES. Structure of the title complex was proposed.展开更多
Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen...Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen) or 2,2'-bipyridyl (bpy). The temperature dependence of the magnetic susceptibility of ([Gd(phen)(2)(ClO4)](2)[Cu(pbaOH)])(ClO4)(2) has been studied in the 4-300K range, giving the exchange integral J = 6.69 cm(-1). This indicates a weak ferromagnetic interaction between the copper(II) and gadolinium(III) ions.展开更多
Co3(S2C6H4)3{P(C4H9)3}3 ·2CH2Cl2, Mr = 1373. 45, mono-clinic, space group P21/c, a = 16. 110(5), b=36.313(10), c=13. 502(5) A , β= 105. 69(4)% V=7604. 4 A3, Z = 4, Dc = 1. 20 g. cm-3, μ=10. 03 cm-1, and F (000)...Co3(S2C6H4)3{P(C4H9)3}3 ·2CH2Cl2, Mr = 1373. 45, mono-clinic, space group P21/c, a = 16. 110(5), b=36.313(10), c=13. 502(5) A , β= 105. 69(4)% V=7604. 4 A3, Z = 4, Dc = 1. 20 g. cm-3, μ=10. 03 cm-1, and F (000) = 2990. R(Rw) is 0. 086(0. 091) for 4559 observed unique reflections. The three cobalt atoms in the complex form an isosceles triangle with an average Co -Co bond distance of 2. 504(5) A. The average values of Co - S and Co - P bond distances are 2. 271(7) A , and 2. 198(8) A , respectively.展开更多
The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5...The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5), c=15. 581 (3)A. V=6095(3) A, Z=8,M.=863. 12, Dc=1.881 g/cm3; u=19. 24 cm-1 and F(000) = 3376. The final refinement of 2455 observed reflections is converged with R= 0. 043 and Rw=0.047. X-ray crystal structure analysis revealed that the coordinationgeometry of Hg atom is a distorted tetrahedron with two Hg-N bonds and two Hg- S bonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is cryordianted to the Hg aotm uia the mercapto sulphur and the β-nitrogen atoms.展开更多
Theories based on the isotropic Heisenberg model have been adjusted to the study of magnetic properties in exchange coupled unsymmetrical trinuclear complexes.Program for theoretical fitting of the variable-temperatur...Theories based on the isotropic Heisenberg model have been adjusted to the study of magnetic properties in exchange coupled unsymmetrical trinuclear complexes.Program for theoretical fitting of the variable-temperature magnetic susceptibility has been set up to produce coupling constants and spin states of the magnetic centers.Calculation has been carried out on a series of Co(Ⅱ)complexes containing mixed thiolato and phosphine ligands:Co3(mp)2(mpH)2(PR3)3(R=Et,R=Bu) and Co3(bdt)3 (PBu3)3.It has been found that all these studied complexes are anti-ferromagnetically coupled.Coupling constant shows the strength of the exchange interaction,which is determined by many factors.Relation between the spin state and the coordination circumstance of Co(Ⅱ) was discussed too.展开更多
The crystal structures of two new trinuclear Mo-S cluster compounds[Mo3S7(TDT)3](Et4N)2·DMF1 and[Mo3S3(O)2(TDT)3](Et4N)2 2 with bianion TDT(S2C6H3CH32-) as ligands are reported in this paper.There is a weak inter...The crystal structures of two new trinuclear Mo-S cluster compounds[Mo3S7(TDT)3](Et4N)2·DMF1 and[Mo3S3(O)2(TDT)3](Et4N)2 2 with bianion TDT(S2C6H3CH32-) as ligands are reported in this paper.There is a weak interaction between the cluster anions through S atoms(μ-S or S of TDT ligands) in each unit cell of these two compounds.Moreover,the mutual transformation between these two compounds by the cluster reaction is discussed.Crystal data:for 1 space group=P1,a=12.996(4),b=18.100(8),c=12.530(4),α=91.57(3),β=97.42(3),γ=69.04(3)°,Z=2,5309 reflections,R=0.052;for 2 space group C2/c,a=26.504(9),b=22.177(5),c=17.355(9),β=108.43(9)°,Z=8,2999 reflections,R=0.079.展开更多
The crystal of the title complex with formula C48H52N8O16CI2Cd3(Mr=1405. 10) was crystallized in monoclinic, space group P21/n, with a=12. 666 (3), b=18. 306(6), c=13. 231 (4) A, p=111. 68(3), V=2851 (2) A3, Z=2, Dr=1...The crystal of the title complex with formula C48H52N8O16CI2Cd3(Mr=1405. 10) was crystallized in monoclinic, space group P21/n, with a=12. 666 (3), b=18. 306(6), c=13. 231 (4) A, p=111. 68(3), V=2851 (2) A3, Z=2, Dr=1. 637 g/cm-3 p=12. 680 cm-1, F(000)=1404. The final refinement is convergedwith R=0. 052 and Rw=0. 055. In the molecule [Cd3(py8(Oac)4] (CIO4)2, the aver-age values of Cd-N and Cd-O bonds are 2. 306 and 2. 288 A, respectively. In thecanon of the title complex. each Cd atom is coordinated by N and O atoms, which arefrom pyridine molecules and acetatoes, respectively, to form a distorted octahedron.And three Cd atoms are linked by two u2-O atoms of two acetatoes and other two u-ac-etato side bridges.展开更多
In the paper,we report a highly robust and porous bimetallic Ti-MOF(designated Mg_(2)Ti-ABTC)by utiliz-ing a trinuclear[Mg_(2)TiO(COO)_(6)]cluster and a tetradentate H_(4)ABTC(3,3′,5,5′-azobenzene tetracarboxylic ac...In the paper,we report a highly robust and porous bimetallic Ti-MOF(designated Mg_(2)Ti-ABTC)by utiliz-ing a trinuclear[Mg_(2)TiO(COO)_(6)]cluster and a tetradentate H_(4)ABTC(3,3′,5,5′-azobenzene tetracarboxylic acid)ligand.Mg_(2)Ti-ABTC exhibited permanent porosity for N_(2),CO_(2),CH_(4),C_(2)H_(2),C_(2)H_(4),and C_(2)H_(6)gas adsorption.Further-more,Mg_(2)Ti-ABTC exhibited outstanding photocatalytic activity in the oxidation of aromatic sulfides to the corre-sponding sulfoxides under ambient air conditions.Mechanism studies reveal that photoinduced holes(h^(+)),the super-oxide radical(·O_(2)^(-)),and singlet oxygen(^(1)O_(2))are pivotal species involved in the photocatalytic oxidation reaction.展开更多
Development of transition metal-based photocatalysts with low cost, strong visible light absorption, and high efficiency is a longstand pursuit for advanced organic synthesis, yet remains highly challenging. In this a...Development of transition metal-based photocatalysts with low cost, strong visible light absorption, and high efficiency is a longstand pursuit for advanced organic synthesis, yet remains highly challenging. In this article, an anthraquinone-based copper(I)cyclic trinuclear complex(1) was designed and it featured strong visible light absorption, high charge separation efficiency and photochemical properties. Complex 1 as a heterogeneous photocatalyst can efficiently catalyze homo-coupling of terminal alkynes and denitrification-oxidative coupling reaction between hydrazinopyridine and terminal alkynes with excellent yield(up to 99%), broad substrate tolerance(27 examples) and superior reusability(up to 10 cycles without loss of performance) under mild conditions.展开更多
基金Supported by the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.14HASTIT017)the Program for Innovative Research Team(in Science and Technology)in University of Henan Province(No.14IRTSTHN008)+1 种基金the Foundation of Education Committee of Henan Province(No.142300410301)the National Natural Science Foundation of China(No.21571093)
文摘Two new coordination polymers,named {[Co3（pfca）6（phen）2]·2H2O}n（1） and[Cu（pfca）2（4,4＇-bpy）（H2O）]n（2）（Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine）,were hydrothermally synthesized and characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 crystallizes in the triclinic crystal system,space group P1 with a = 10.939（3）,b = 12.430（4）,c = 13.815（4） A,α=78.436（3）,β= 70.261（3）,γ= 80.268（3）°,V= 1721.8（9） A^3,Dc = 1.508 g/cm^3,Mr= 1564.06,Z = 1,F（000） = 799,μ= 0.802 mm^（-1）,the final R = 0.0432 and wR = 0.1015 for 13250 observed reflections with I 2σ（I）.Complex 2 is of monoclinic system,space group P2／lc with a =15.4985（14）,b = 15.8424（14）,c = 10.9528（10） A,β= 107.1600（10）°,V= 2569.6（4） A^3,Dc = 1.468g/cm^3,Mr = 568.02,Z = 4,F（000） = 1164,μ= 0.906 mm^（-1）,the final R = 0.0371 and wR = 0.0842 for 18183 observed reflections with I〉 2σ（I）.Complex 1 features linear Co（Ⅱ）-trinuclear units,which are assembled into a final 3D supramolecular structure through π…π stacking interactions and F-H weak interactions.Complex 2 consists of 1D polymeric Cu（Ⅱ）-chains that are further cohered together by extensive H-bonds.
基金Supported by the Natural Science Foundation of Hunan Province(No.11JJ9006)Hunan Provincial innovative platform open fund project(11K009)Science and Technology Committee of Hunan Province(2012WK3029,2012GK3031)
文摘A novel complex Mn3（2,2＇-bipy）ff3,5-DMBA）6 with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＇-bipyridine （2,2＇-bipy） has been synthesized by means of a solvent method. It crystallizes in the monoclinic space group C2/c with a = 3.1118（6）, b = 1.1754（2）, c = 2.0887（4） nm, β = 118.50（3）°, V= 6.714（2） nm3, Dc = 1.384 g/cm3, Z = 8, F（000） = 2912, the final GOOF = 1.078, R = 0.0691 and wR = 0.1455. The crystal structure shows that the three coordinated manganese（II） ions lie in a line with the middle one as the symmetric center. The distance between the central manganese（II） and the symmetric one is 0.3549 nm. There exist two coordination modes for the three manganese （II） ions： the symmetric manganese（II） ions are coordinated with three oxygen atoms and two nitrogen atoms from three 3,5-DMBA molecules and one 2,2＇-bipy molecule, respectively, forming a distorted square-pyramidal coordination geometry; the middle manganese（II） ion is coordinated with six oxygen atoms from six 3,5-DMBA molecules, generating a distorted octahedral coordination geometry. Spectrum properties of the complex were also studied.
基金Supported by the Foundation of Fujian Educational Committee, China (No. JB10007 and JB10004)
文摘A novel trinuclear nickel（II） complex [Ni3（bushz）z（Himdz）2（H20）2].2DMF （1, bushz = N-butylsalicylhydrazide, Himdz = imidazole, DMF = N,N-dimethyl-forrnamide） has been synthesized and characterized by X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P2 1/c with a = 7.706（7）, b = 14.882（6）, c = 18.639（6） A, β = 108.08（2）°, V= 2032（1） A3, Dc = 1.525 g/cm3, Mr = 932.95, Z= 2, F（000） = 972,μ = 1.442 mm-1, the final R = 0.0359 and wR = 0.0771. The three nickel（II） atoms in 1 are arranged in a strictly linear structure and exhibit alternating square-planar and octahedral geometries. The complex is connected to form a supramolecule with an infinite three-dimensional network through intermolecular hydrogen bonds. The electrochemical studies reveal that redox of Ni3＋/Ni2＋ in the complex is a quasi-reversible process. The thermal stability of the title complex was also studied.
文摘A Schiff base ligand（H2CSF,C13H11NO4,1） derived from 3-carboxylsalicylaldehyde and furfurylamine,and its trinuclear complex [Ni3（CSF）2（CH3COO）2（DMF）2（H2O）2]（2） were synthesized.Compound 1 was characterized by elemental analysis,1H NMR,IR,MS and X-ray diffraction analysis.The crystal of 1 belongs to the monoclinic system,space group P21/c with a = 8.472（2）,b = 19.743（5）,c = 7.2300（18） ,β = 110.278（4）°,V = 1134.4（5） 3,Z = 4,Mr = 245.23,Dc = 1.436 g·cm-3,μ = 0.108 mm-1,F（000） = 512,λ = 0.71073 ,the final R = 0.0440 and wR = 0.1199 for 1426 observed reflections（I 2σ（I））.In the crystal of 1,there exist intramolecular hydrogen bonds and weak intermolecular C-H···O hydrogen bonds.Compound 2 was characterized by elemental analysis,IR,TG and X-ray diffraction analysis.The crystal of 2 is of triclinic system,space group P1 with a = 10.1237（17）,b = 10.4086（18）,c = 10.4884（18） ,α = 82.528（2）,β = 67.339（2）,γ = 83.010（2）°,V = 1008.1（3） 3,Z = 1,Mr = 962.87,Dc = 1.586 g·cm-3,μ = 1.463 mm-1,F（000） = 498,λ = 0.71073 ,the final R = 0.0517 and wR = 0.0805 for 2065 observed reflections（I 2σ（I））.The geometry of the trinuclear molecule is centrosymmetric,in which every Ni（Ⅱ） ion is coordinated in a slightly distorted octahedron.The three Ni（Ⅱ） ions are arranged in a straight line.The two CSF2-ions act as NOO tridentate ligands with the phenolate and carboxylate oxygen as bridging atoms.The coordination atoms of CSF2-anions and water molecules are coordinated on the equatorial plane,while the two bridging acetate ions and two DMF are trans-coordinated on the apical sites.
基金conducted in the framework of a project sponsored by the National Natural Science Foundation of China(No.21071100)Liaoning Baiqianwan Talents Program and the LNET(LJQ2011038)
文摘The coordination polymer, [Mn3（bpta）2（bip）2], （H3bpta = biphenyl-3,3＇,5-tricar- boxylic acid, bip = 2,6-bis（imidazole-1-yl）pyridine）, has been synthesized under hydrothermal con- ditions and characterized by elemental analysis, FT-IR, XRD, TGA and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.919（3）, b = 9.780（2）, c = 20.352（7） A, V = 2344.4（10） A3, Z= 2, C52H32Mn3N10012, Mr = 1153.70, Dc = 1.634 g/cm3, p（MoKa） = 0.876 mm-1, F（000） = 1170, the finalR = 0.0605 and wR = 0.1177. The complex forms a 2D layer with trinuclear Mn（II） units and further assembles into a 3D supramolecular network structure through C-H..＇O hydrogen bonding and C-H...π interactions. Moreover, the negative J value indicates the presence of antiferromagnetic coupling between the Mn（II） ions within a trinuclear unit.
基金Supported by the Natural Science Foundation of Hunan Province (No. 11JJ9006)Science and Technology Committee of Hengyang (2011kj25)
文摘A three-dimensional framework copper（Ⅱ） coordination polymer with copper carbonate basic and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） has been hydrothemally synthesized.The complex （2,C14 H10 CuN8 ·3H2 O） crystallizes in tetragonal,space group P4 2 /n,a=2.08581（12）,b=2.08581（12）,c=0.72331（4） nm,M r=761.73,V=3.1468（3） nm 3,Dc=1.608 g/cm 3,Z=4,F（000）=1552,GOOF=1.07,R=0.0515 and wR=0.1689.Every asymmetric unit molecular structure of the complex is composed with one copper ion,one and half water molecules and two Hpt molecules.Each copper ion is coordinated with five nitrogen atoms from four Hpt molecules,forming a distorted square pyramidal geometry.The fluorescence spectrum analysis shows that the title complex at room temperature exhibits intense photoluminescence with maximum emission at 450 nm.The quantum chemistry calculation study on the complex has been performed.The stability,some frontier molecular orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.
文摘In this paper detailed studies of the cyclic voltammetry(CV) of trinuclear metal cluster compounds [M_3O_2(O_2CCH_3,)6(H,O),j z+ (M,=Mo3,MoW2,W3) are reported.The result of CV shows that they are similar to each other.There are a reversible redox peak near-0. 48 V and an irreversible reduced peak near-1.10 V in the scan range of + l.0 V to l. 5 V.It implies that the M_3O_2,clusters might gain one electron to be further reduced.But the two-electron-reduced product of M_3O_2 clusters are instable.The theoretical calculations(EHMO) agree well with the result of the CV experiment.
基金Supported by the 973 Program (2007CB815301 and 2006CB932904)the National Natural Science Foundation of China (20333070, 20871114 and 20673118)+1 种基金the Science Foundation of CAS (KJCX2-YW-M05)Fujian Province (2006F3132 and 2007J0171)
文摘Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,10-phenanthroline, Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, and DMF = N,N-dimethylformamide） have been synthesized by using mononuclear [Fe（Phen）2（CN）2]·2H2O and [Fe（bpy）2（CN）2]·3H2O as precursors. These two complexes crystallize in monoclinic space groups P21/c and C2/c, respectively. For 1, a = 25.164（2）, b = 12.0405（11）, c = 20.4433（15） A, β = 91.948（3）°, V = 6190.5（9） A^3, Z = 4, Mr = 1418.90, Dc = 1.522 g/cm^3, F（000） = 2936, μ = 1.161 mm^-1, the final R = 0.0722 and wR = 0.2011 for 10779 observed reflections （I 〉 2σ（I））. For 2, a = 43.5945（0）, b = 11.8447（0）, c = 29.5637（2）A, β = 120.430（11）o, V = 13162.76（9） A^3, Z = 8, Mr = 1518.48, Dc = 1.533 g/cm^3, F（000） = 6288, μ = 1.101 mm^-1, the final R = 0.0711 and wR = 0.1783 for 11262 observed reflections （I 〉 2σ（I））.
基金Supported by the National Natural Science Foundation of China(Nos.20371028and20671052).
文摘Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu（Ⅱ）and Zn（Ⅱ）] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate（HPNP）.The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.
基金Supported by the Institute Foundation of Siping City (No.2009011)
文摘The coordination polymer,[Mn3（L） 2（adip） 3]·2H2O（L = 2-（4-fluorophenyl） -1H-imidazo[4,5-f] [1,10]phenanthroline and H2adip = adipic acid） ,has been synthesized under hydro-thermal conditions and characterized by elemental analysis,IR and single-crystal X-ray diffraction. It crystallizes in triclinic,space group P1^- with a = 8.4085（11） ,b = 11.1273（14） ,c = 14.5758（18） ,α = 78.528（2） ,β = 75.425（2） ,γ = 78.143（2） °,V = 1276.0（3） A^3,Z = 1,C56H50F2Mn3N8O14,Mr = 1261.86,Dc = 1.642 g/cm^3,F（000） = 647,μ（MoKa） = 0.819 mm^-1,R = 0.0446 and wR = 0.1008. The backbones of the two types of adip dianions link the neighboring trinuclear Mn（Ⅱ） clusters to yield a two-dimensional layer structure. The large conjugated L ligands are located on both sides of the two-dimensional layers. Additionally,the O-H···O,O-H···N and N-H···O hydrogen bonds further stabilize the structure.
基金Supported by the Construct Program of the Key Discipline in Hunan Province and Key Project of Production Plan of Hengyang City(2013)
文摘A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and water. It crystallizes in the monoclinic space group C2/c with a = 31.1497（15）, b = 11.7576（6）, c = 20.9049（10） A, fl = 118.4550（10）°, V- 6731.4（6） A3, Dc = 1.412 g/cm3, Z = 4, F（000） = 2972, GOOF = 1.069, the final R= 0.0667 and wR= 0.1917. The whole molecule consists of three zinc ions, six 3,5-DMBA molecules, two 2,2＂-bipyridine molecules and one and half water molecules, in which three zinc ions are bridged by six μ2-η1：η0 carboxylate groups of 3,5-DMBA. The Zn（1） atom is centrosymmetric, and adopts a distorted octahedral ZnO6 geometry, while the Zn（2） gives a distorted square pyramidal ZnOsN2 geometry. The spectroscopic characterization and thermal stability properties of the complex were investigated.
文摘By the reaction of bidentate ligand 1,1'-bis(diphenylphosphino)-ferrocene (dppf) with MoCl_4(CH_3CN)_2, a novel bonding type complex (MoCl_4)2_· (dppf) was synthesized and characterized by elemental analyses, ^(31)p-NMR, IR and electronic spectra, TG and ICP-AES. Structure of the title complex was proposed.
文摘Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen) or 2,2'-bipyridyl (bpy). The temperature dependence of the magnetic susceptibility of ([Gd(phen)(2)(ClO4)](2)[Cu(pbaOH)])(ClO4)(2) has been studied in the 4-300K range, giving the exchange integral J = 6.69 cm(-1). This indicates a weak ferromagnetic interaction between the copper(II) and gadolinium(III) ions.
文摘Co3(S2C6H4)3{P(C4H9)3}3 ·2CH2Cl2, Mr = 1373. 45, mono-clinic, space group P21/c, a = 16. 110(5), b=36.313(10), c=13. 502(5) A , β= 105. 69(4)% V=7604. 4 A3, Z = 4, Dc = 1. 20 g. cm-3, μ=10. 03 cm-1, and F (000) = 2990. R(Rw) is 0. 086(0. 091) for 4559 observed unique reflections. The three cobalt atoms in the complex form an isosceles triangle with an average Co -Co bond distance of 2. 504(5) A. The average values of Co - S and Co - P bond distances are 2. 271(7) A , and 2. 198(8) A , respectively.
文摘The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5), c=15. 581 (3)A. V=6095(3) A, Z=8,M.=863. 12, Dc=1.881 g/cm3; u=19. 24 cm-1 and F(000) = 3376. The final refinement of 2455 observed reflections is converged with R= 0. 043 and Rw=0.047. X-ray crystal structure analysis revealed that the coordinationgeometry of Hg atom is a distorted tetrahedron with two Hg-N bonds and two Hg- S bonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is cryordianted to the Hg aotm uia the mercapto sulphur and the β-nitrogen atoms.
文摘Theories based on the isotropic Heisenberg model have been adjusted to the study of magnetic properties in exchange coupled unsymmetrical trinuclear complexes.Program for theoretical fitting of the variable-temperature magnetic susceptibility has been set up to produce coupling constants and spin states of the magnetic centers.Calculation has been carried out on a series of Co(Ⅱ)complexes containing mixed thiolato and phosphine ligands:Co3(mp)2(mpH)2(PR3)3(R=Et,R=Bu) and Co3(bdt)3 (PBu3)3.It has been found that all these studied complexes are anti-ferromagnetically coupled.Coupling constant shows the strength of the exchange interaction,which is determined by many factors.Relation between the spin state and the coordination circumstance of Co(Ⅱ) was discussed too.
文摘The crystal structures of two new trinuclear Mo-S cluster compounds[Mo3S7(TDT)3](Et4N)2·DMF1 and[Mo3S3(O)2(TDT)3](Et4N)2 2 with bianion TDT(S2C6H3CH32-) as ligands are reported in this paper.There is a weak interaction between the cluster anions through S atoms(μ-S or S of TDT ligands) in each unit cell of these two compounds.Moreover,the mutual transformation between these two compounds by the cluster reaction is discussed.Crystal data:for 1 space group=P1,a=12.996(4),b=18.100(8),c=12.530(4),α=91.57(3),β=97.42(3),γ=69.04(3)°,Z=2,5309 reflections,R=0.052;for 2 space group C2/c,a=26.504(9),b=22.177(5),c=17.355(9),β=108.43(9)°,Z=8,2999 reflections,R=0.079.
文摘The crystal of the title complex with formula C48H52N8O16CI2Cd3(Mr=1405. 10) was crystallized in monoclinic, space group P21/n, with a=12. 666 (3), b=18. 306(6), c=13. 231 (4) A, p=111. 68(3), V=2851 (2) A3, Z=2, Dr=1. 637 g/cm-3 p=12. 680 cm-1, F(000)=1404. The final refinement is convergedwith R=0. 052 and Rw=0. 055. In the molecule [Cd3(py8(Oac)4] (CIO4)2, the aver-age values of Cd-N and Cd-O bonds are 2. 306 and 2. 288 A, respectively. In thecanon of the title complex. each Cd atom is coordinated by N and O atoms, which arefrom pyridine molecules and acetatoes, respectively, to form a distorted octahedron.And three Cd atoms are linked by two u2-O atoms of two acetatoes and other two u-ac-etato side bridges.
文摘In the paper,we report a highly robust and porous bimetallic Ti-MOF(designated Mg_(2)Ti-ABTC)by utiliz-ing a trinuclear[Mg_(2)TiO(COO)_(6)]cluster and a tetradentate H_(4)ABTC(3,3′,5,5′-azobenzene tetracarboxylic acid)ligand.Mg_(2)Ti-ABTC exhibited permanent porosity for N_(2),CO_(2),CH_(4),C_(2)H_(2),C_(2)H_(4),and C_(2)H_(6)gas adsorption.Further-more,Mg_(2)Ti-ABTC exhibited outstanding photocatalytic activity in the oxidation of aromatic sulfides to the corre-sponding sulfoxides under ambient air conditions.Mechanism studies reveal that photoinduced holes(h^(+)),the super-oxide radical(·O_(2)^(-)),and singlet oxygen(^(1)O_(2))are pivotal species involved in the photocatalytic oxidation reaction.
基金Guo-Hong Ning is thankful for the support from the Guangdong Basic and Applied Basic Research Foundation (2019B151502024)the Guangzhou Science and Technology Project (202201020038)+1 种基金supported by the National Natural Science Foundation of China (22371091, 21975104, 22150004, 22101099)the Guangdong Major Project of Basic and Applied Research (2019B030302009)。
文摘Development of transition metal-based photocatalysts with low cost, strong visible light absorption, and high efficiency is a longstand pursuit for advanced organic synthesis, yet remains highly challenging. In this article, an anthraquinone-based copper(I)cyclic trinuclear complex(1) was designed and it featured strong visible light absorption, high charge separation efficiency and photochemical properties. Complex 1 as a heterogeneous photocatalyst can efficiently catalyze homo-coupling of terminal alkynes and denitrification-oxidative coupling reaction between hydrazinopyridine and terminal alkynes with excellent yield(up to 99%), broad substrate tolerance(27 examples) and superior reusability(up to 10 cycles without loss of performance) under mild conditions.
