四苯骈卟啉及其金属配合物的合成

卟啉类化合物作为电子给体在光合作用模拟研究中占据着重要位置 ,在卟啉环上引入供电子基团以增大共轭体系 ,常有利于卟啉环的给电子作用 ,过去常用的卟啉化合物为四苯基卟啉及其衍生物 ,但由于空阻作用 ,四个亚甲基上的苯基不能很好与卟啉环共平面而降低了共轭效应 ,为了寻求一种更有利于卟啉环共轭大Π键形成的结构 ,我们合成了比四苯基卟啉共平面效果更好的卟啉化合物———四苯骈卟啉 (Ｈ2 ＴＢＰ)及其与Ｎｉ2 + 、Ｃｏ2 + 、Ｚｎ2 + 的金属配合物以及研究它的给电子作用效果。四苯骈卟啉配合物早在 1 92 8年就为人们所认识[1] ,但其研…     

Syntheses,urease inhibition activities,and fluorescent properties of transition metal complexes

Four transition metal complexes with Schiff base and 1,10-phenanthroline, [Cu(L)(phen)]₂·C₂H₅OH (1), [Zn(L)(phen)]₂·C₂H₅OH (2), [Ni(L)(phen)]₂·C₂H₅OH (3), and [Co(L)(phen)]₂·C₂H₅OH (4) (H₂L?=?1-((2-hydroxynaphthalen-1-yl)methylene)thiosemicarbazide; phen?=?1,10-phenanthroline) were synthesized and characterized by physico-chemical methods. The crystal structure of 1 was determined by X-ray single-crystal diffraction analysis. 1 crystallizes in the orthorhombic space group Pbca with a?=?15.008(9), b?=?16.100(10), c?=?37.54(2)?Å, V?=?9070(10)?ų, Z?=?8, GOOF?=?1.002, R ₁?=?0.0626, and wR ₂?=?0.0912. The fluorescence and urease inhibitory activities of the compounds were tested. The enzymatic activity study indicated that 3 possessed potent inhibition against jack bean urease, with IC₅₀?=?1.2?±?0.1?μM, and about 35 times more than 42.1?±?0.4 acetohydroxamic acid as positive reference. This suggests that inhibitory efficiency of these complexes can be strongly influenced by different transition metal ions.     

Phenanthroline complexes of zinc and calcium carbamates

Bis(N,N‐di‐n‐butyl­di­thio­carbamato‐κ²S,S′)(1,10‐phenanthroline‐κ²N,N′)­zinc(II) ethanol hemisolvate, [Zn(C₉H₁₈NS₂)₂(C₁₂H₈N₂)]·0.5C₂H₆O, (I), and bis(N,N‐di‐n‐hexyldithiocarbamato‐κ²S,S′)­bis(1,10‐phenanthroline‐κ²N,N′)calcium(II), [Ca(C₁₃H₂₆NS₂)₂(C₁₂H₈N₂)₂], (II), are mixed‐ligand com­plexes. In the first compound, the Zn atom has a distorted octahedral coordination, while in the second compound, the Ca atom is eight‐coordinate, with four S and four N atoms forming a highly distorted cube.     

Syntheses and characterizations of group 6 metal cyanotrihydroborate complexes

The anions, [M(CO)_6-n(NCBH₃)_n]ⁿ⁻ (n=2, M=Cr(1); n=3, M=Cr(2), Mo(3), W(4)), were prepared either from the reactions of sodium cyanotrihydroborate with group 6 transition metal hexacarbonyls, M(CO)₆ (M=Cr, Mo, W), or through the reactions of M(CO)₃(CH₃CN)₃ (M=Cr, W) with sodium cyanotrihydroborate. The cyanotrihydroborate ligand bonds to the metal through a nitrogen atom, which was confirmed by the Infrared, proton and boron NMR spectroscopies. Crystal structures of the above complexes were determined by single crystal X-ray diffraction analyses. A cis configuration is found in 1. Molecular structures of 2, 3, and 4 are similar and a facial configuration is observed.     

Syntheses and X-ray structures of some pyrrolylaldiminate metal complexes

Several pyrrolylaldiminate complexes of Group 1, 4 and 13 metals are reported. The reaction of 5-tert-butyl-2-[(2,6-diisopropylphenyl)aldimino]pyrrole (HL) with NaH produced LNa(THF) (1). In situ lithiation of HL followed by addition of one equivalent of MCl_x (M=Zr, x=4; M=Hf, x=4, M=Al, x=3) afforded the corresponding pyrrolylaldiminate complexes, MLCl₂(μ-Cl)₂Li(OEt₂)₂ (M=Zr, 3; Hf, 4) and AlLCl₂ (5). Alkylation of 5 with MeMgBr generated AlLMe₂ (6). In addition to the spectroscopic data, complexes 3-6 were characterized by X-ray crystallography.     

Syntheses, emission properties and intramolecular ligand exchange of zinc complexes with ligands belonging to the tmpa family

The zinc complexes [(L1)(2)Zn(MeOH)(2)](OTf)(2), [(L1)ZnCl(2)], [(L2)ZnCl(2)], [(L2)Zn(OTf)(H(2)O)]OTf and [(Me-bispic)ZnCl(2)] of the ligands N-[(2-pyridyl)methyl]-2,2'-dipyridylamine (L1), N-[bis(2-pyridyl)methyl]-2-pyridylamine (L2) and N-methyl-[bis(2-pyridyl)methyl]amine (Me-bispic) were synthesised and characterised. The first copper(I) complexes of the ligands L1 and L2 were also synthesised and structurally characterised. [(L1)ZnCl(2)] showed unexpected fluxional behaviour in solution and revealed an interesting intramolecular ligand exchange mechanism in the coordination sphere of the zinc ion. Furthermore, strong blue emission was observed under UV-light excitation.     

Syntheses and crystal structure studies of two zinc complexes of enoxacin

Two zinc complexes of enoxacin were synthesized and their crystal structures were determined. Compound 1, [Zn(H-Eno) · Cl₂] · 3H₂O (H-Eno = Enoxacin), crystallizes in the triclinic system, space group P 1, with lattice parameters a = 8.7731(12), b = 9.4976(14), and c = 13.2033(19) Å, α = 86.319(7)°, β = 71.912(7)°, and γ = 80.604(7)°, V = 1031.6(3) ų, Z = 2, D _Calcd = 1.631 Mg m^?3; compound 2, [Zn(H-Eno) · (H₂O)₂] · 2NO₃, also crystallizes in the triclinic system, space group P 1, with lattice parameters a = 8.751(2), b = 9.014(2), and c = 12.594(3) Å, α = 92.277(14)°, β = 109.867(12)°, and γ = 111.469(12)°, V = 854.1(3) ų, Z = 1, D _Calcd = 1.684 Mg m^?3.     

Syntheses and NLO properties of metal alkynyl dendrimers

Metal-containing (particularly organometallic) dendrimers are briefly introduced, the origin of nonlinear optical (NLO) effects in molecules is briefly summarized, and the syntheses of metal alkynyl dendrimers and progress in employing metal alkynyl dendrimers as NLO materials are reviewed.     

Syntheses,structures, and luminescent properties of zinc(II) complexes based on imidazole derivative

Two new Zn(II) coordination complexes [ZnL₂(SCN)₂] (I) and [ZnL₂Cl₂] (II) have been pre-pared by self-assembly of corresponding metal salts with (E)-2-(3-(4-(1H-imidazole-1-yl)styryl)-5,5-dimethylcyclohexo-2-enylidene) malononitrile (L) and characterized by IR spectrum, elemental analysis and single-crystal X-ray diffraction. Complexes I and II are two-dimensional (2D) networks with different topology structures. The luminescence properties were investigated.     

Syntheses,structures and properties of four second-sphere coordination complexes via metal halide anion and naphthalene-based ligand

Second-sphere coordination refers to any intermolecular interactions with the ligands directly bound to the primary coordination sphere of a metal ion. Four supramolecular complexes, 0.5[L·2H]²⁺·0.5[MCl₄]^2?·[CH₃OH]·0.5[CH₂Cl₂] (M = Co, crystal 1; M = Mn, crystal 2), 0.5[L·2H]²⁺·0.5[ZnBr₄]^2?·[CH₃OH]·0.5[CH₂Cl₂] (crystal 3), and 0.5[L·2H]²⁺·0.5[Cu₂Br₄]^2?·H₂O (crystal 4), based on naphthalene-based ligand N,N,N′,N′-tetra-p-methylnaphthyl-ethanediamine (L), have been synthesized. X-ray analysis reveals that 1–3 are isostructural, in which the methanol molecules are bridges, connecting the protonated L and metal chloride anions via N–H?O and O–H?Cl (Br) interactions to construct the host framework, and forming X-shaped cavity accessible for the inclusion of weakly polar guest molecules of dichloromethane. Dichloromethane is connected with the host framework through van der Waals forces. In 4, a dinuclear anion [Cu₂Br₄]^2? is connected with the ligand through N–H?Br interactions, in which the water molecules are accommodated between chains formed by the ligand and [Cu₂Br₄]^2?. Structure stability, thermal analysis, and photoluminescent properties were studied for 1–4.     

Syntheses,structural characterization,and thermal behaviour of metal complexes with 3-aminopyridine as co-ligands

Transition Metal Chemistry - Six mixed metal complexes with 3-aminopyridine (3-ampy) as a co-ligand have been synthesized: catena-{[M(μ2-3-ampy)(H2O)4]SO4·H2O} (M=Ni (1) and Co (2)),...     

Syntheses,crystal structures and photocatalytic properties of transition metal complexes based on 9,10-anthraquinone-1,3-dicarboxylate

Transition Metal Chemistry - Five transition metal complexes based on the ligand 9,10-anthraquinone-1,3-dicarboxylate acid (1,3-H2AQDC) have been synthesized and characterized by...     

Syntheses,crystal structures,and electrochemical properties of transition metal complexes with new tetrathiafulvalene-derivatized acetylacetonate ligands

Two new tetrathiafulvalene (TTF) derivatives of acetylacetone, namely, 3-[{6,7-benzo-2-(methylthio)-TTF-3-yl}-thio]-2,4-pentanedione (L₁) and 3-[{6,7-(ethylenedithio)-2-(methylthio)-TTF-3-yl}-thio]-2,4-pentanedione (L₂), have been synthesized. Four transition metal(II) complexes of these ligands, of general formulae [Zn(L₁)₂(THF)₂] and [M(L₂)₂(THF)₂] (M = Zn, Mn, and Ni), have been prepared and structurally characterized. The redox properties of both the ligands and their complexes were investigated by cyclic voltammetry. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. Peng Zheng and Yun-Jun Guo contributed equally to this work.     

Photochemical and chemical oxidation of alpha-dimine-dithiolene metal complexes: insight into the role of the metal atom

[Pd(bpy)(bdt)], 2 (bpy = 2,2'-bipyridine, bdt = 1,2-benzenedithiolate), was prepared in good yield by the reaction of bdtNa2 with [(bpy)PdCl2] in DMSO. The analogous nickel complex, 1, was prepared in a similar reaction using MeOH/CH2Cl2 and [(bpy)NiCl2.dmf]2. Both 1 (a = 7.9920(1) A, b = 11.4385(1) A, c = 16.1415(1) A, beta = 103.327(1) degrees, V = 1435.86(2) A3, Z = 4) and 2 (a = 8.1631(5) A, b = 11.4379(7) A, c = 16.2475(10) A, beta = 103.7010(10) degrees, V = 1473.84(12) A3, Z = 4) crystallize in the monoclinic space group P2(1)/c and are isostructural with their previously reported platinum analogue. In accord with the results observed for platinum but not nickel, photochemical oxidation of 2 in DMF provides the monosulfinate complex [Pd(bpy)(bdtO2)], 4, along with a minor amount of the corresponding disulfinate [Pd(bpy)(bdtO4)], 5, while chemical oxidation yields only the latter. 4 cocrystallizes with 5 in the monoclinic space group P2(1)/c (a = 8.026(3) A, b = 14.600(6) A, c = 13.371(3) A, beta = 101.80(3) degrees, V = 1533.8(9) A3, Z = 4) as does pure 5 (a = 8.5611(9) A, b = 14.4586(15) A, c = 13.3677(14) A, beta = 108.122(2) degrees, V = 1572.6(3) A3, Z = 4). Comparison of spectroscopic and electrochemical properties of the three complexes, [M(bpy)(bdt)], yields the following ordering for the energy of the HOMO: Pd < Ni < Pt. The observed reactivity patterns and the electronic data suggest that the "anomalous" reactivity of 1 be attributed to the greater relative flexibility of the coordination geometry for nickel(II) complexes rather than electronic differences such as the energies of the frontier orbitals.     

Syntheses,crystal structures and properties of four metal coordination complexes constructed from aromatic carboxylate and benzimidazole-based ligands

Transition Metal Chemistry - Four metal–organic coordination complexes, namely {[Zn(SIP)(mbi)2]·(Hmbi)·(H2O)2}n (1), {[Cd3(SIP)2(bbhb)3(H2O)4]·(H2O)2}n (2),...     

Syntheses, structures, and optical properties of novel zinc(ii) complexes with multicarboxylate and N-donor ligands

Five novel coordination polymers [Zn(2)(OA)(4,4'-bipy)(H(2)O)].0.5(4,4'-bipy), [Zn(2)(OA)(dib)(H(2)O)].H(2)O, [Zn(2)(OA)(bbi)(2)].3H(2)O, [Zn(2)(OA)(phen)(2)(H(2)O)] and [Zn(4)(OA)(2)(2,2'-bipy)(2)(H(2)O)].2H(2)O were obtained by hydrothermal reactions of Zn(NO(3))(2).6H(2)O with a V-shaped multicarboxylate ligand 3,3',4,4'-oxydiphthalic acid (H(4)OA) and a series of N-donor ligands, namely 4,4'-bipyridine (4,4'-bipy), 1,4-di(1-imidazolyl)benzene (dib), 1,1'-(1,4-butanediyl)bis(imidazole) (bbi), 1,10-phenanthroline (phen), 2,2'-bipyridine (2,2'-bipy). The structures of the complexes were established by single-crystal X-ray diffraction analysis. Complex exhibits a robust 3D porous structure with uncoordinated 4,4'-bipy molecules filling the cavities. Complexes and show a complicated 3D framework, while complexes and have a 2D network and a 1D helical chain structure, respectively. The results indicate that the multicarboxylate OA(4-) ligand can adopt varied coordination modes in the formation of the complexes and the influence of the N-donor ligand on the structure of the complexes is discussed. The photoluminescence properties of H(4)OA and were studied in the solid state at room temperature. Moreover, nonlinear optical measurements showed that displayed a second-harmonic-generation (SHG) response of 0.5 times of that for urea. The results suggested that the configuration and flexibility of the ligands play a key role in directing the related properties of the complexes.     

Structures of bisphosphonate metal complexes: zinc and cadmium complexes of clodronate and its partial ester derivatives

Four new zinc and cadmium bisphosphonates [{NaZn(Cl2CP2O6H)(H2O)5}]n (1), [{Cd2(Cl2CP2O6)(H2O)4}.H2O]n (2), [{Zn(Cl2CP2O6Pri2)(H2O)3}.H2O]n (3), and [{Cd2(Cl2CP2O6Pri2)2(MeOH)2(H2O)2}.H2O]2 (4) have been prepared and their crystal structures determined by single-crystal X-ray diffractometry. Two bisphosphonate ligands were used: clodronate, (dichloromethylene)bis(phosphonate) and its symmetrical P,P'-diisopropyl ester derivative. The structure of the Zn complex 1 is three-dimensional, consisting of one-dimensional Zn-clodronate chains connected to the three-dimensional network by Na+ ions. The structure of Cd complex 2 consists of double layers, and a unique bond was found between the Cd2+ cation and a Cl atom of clodronate. Zn complex 3 consists of one-dimensional chains, but the binding of the bisphosphonate ligands is unique: in 3 the bisphosphonate ligand is only bidentate. Compound 4 is a tetramer, and hydrogen bonds hold the tetramers together, forming a layered structure.     

Syntheses,crystal structures,and properties of four transition metal complexes based on 5-nitro-8-hydroxyquinoline

Four new complexes, [M(C₉H₅N₂O₃)₂(H₂O)₂]·CH₃OH (M?=?Zn(II), Cd(II) and Mn(II)) (1–3) and [Cu(C₉H₅N₂O₃)₂] (4), have been synthesized by reactions of 5-nitro-quinoline-8-yl acetate (NQA) and corresponding metal salts at room temperature and characterized by elemental analysis, IR, thermal gravimetric analysis (TGA), fluorescence measurement and single crystal X-ray diffraction. 1–3 are mononuclear, further extended to 2-D layers by hydrogen bonds. For 4, Cu²⁺ is coordinated by two N atoms and two O atoms from two NQ ligands. TGA indicates that 1–4 have good thermal stabilities. Furthermore, 1 and 2 show excellent luminescence in the solid state at room temperature.