SYNTHESIS, SPECTRAL AND MAGNETIC CHARACTERISATION OF SOME BIMETALLIC ALKOXIDES OF NICKEL(Ⅱ)WITH GALLIUM(Ⅲ)AND ZIRCONIUM(IV)

Some interesting bimetallic isopropoxides of nickel(Ⅱ) with gallium(Ⅲ) and zirconium(Ⅳ), Ni[Ga(OPr~1)_4]_2 and Ni[Zr_2(OPr_1)_9]_2 have been synthesized by the interaction of NiCl_2·2Pr~1OH with K[Ga(OPr~1)_4],and K[Zr_2(OPr~1)_9] respectively, in 1:2 molar ratio. These bimetallic isopropoxides undergo facile alcohol interchange reactions with primary alcohols. However, reactions with tertiary alcohols result in the isolation of partially substituted derivatives with the compositions, Ni[Ga(OPr~1)(OBu~t)_3]_2 and Ni[Zr_2(OPr~1)_3(OBu~t)_6]_2. Characterisation of these derivatives has been made on the basis of elemental analyses, infrared, electronic spectral and magnetic susceptibility measurements. These studies suggest an octahedral geometry for nickel(Ⅱ) in the primary bimetallic alkoxides, while in the case of secondary and tertiary derivatives, an equilibrium is suggested between octahedral and tetrahedral forms.##属性不符     

Syntheses,Crystal Structures,SHG Response and Purple Luminescent Property of Tetra(isothiocyanate) Mn(Ⅱ) and Substituted Benzyl Triphenylphosphonium Cations

Researches on multifunctional molecular materials with both nonlinear optical activity and fluorescence properties have received much interest in molecular chemistry since they have wide application prospects. Here a novel ionic compound 2(BPP)~+·[Mn(NCS)_4]~(2-)(1) was synthesized via the assembly of benzyltriphenylphosphorus chloride, isothiocyanate and manganese chloride, which displays both strong SHG response and purple luminescence. Compound 1 belongs to monoclinic system and crystallizes in Cc space group. X-ray single-crystal diffraction analysis shows that Mn~(2+) ions are tetra-coordinated with N atoms of four NCS-ions through forming a distorted tetrahedral configuration. The anion Mn(NCS)_4~(2-) forms a 1D chain structure through strong S···S interaction. At the same time, there are abundant C–H···S and π···π interactions, which further accumulate into a three-dimensional supramolecular structure. Solid-state fluorescence studies show that the complex 1 has strong purple fluorescence with emission wavelength of 396 nm under excitation wavelength 248 nm. In particular, the second harmonic generation(SHG) measurements show that compound 1 has nonlinear optical activity and its SHG response is 2.25 times that of standard potassium dihydrogen phosphate(KDP). This multifunctional molecular material with SHG response and purple fluorescence is of great significance for the development of new metal organic complexes with potential application prospects.     

Synthesis and Crystal Structure of an Infinite 1D Zigzag Chain Compound (dimbH~+)(ClO_4~-) and Its Comparison with (dimb)2H_2O (dimb = 1,3-Di(imidazol-1-ylmethyl)-5-methylbenzene)

1 INTRODUCTION Recently the rational design and preparation of novel functional materials are one of the highlights in supramolecular chemistry and crystal engi- neering[1]. How to control the molecular structures and topology in the process of self-assembly has attracted extensively attention[2]. To date, a lot of complexes containing well-designed bidentate[3～6], tripodal[7, 8] and hexadentate[9] imidazole moiety ligands have been synthesized by chemists. Some of them have interestin…     

Synthesis,Crystal Structure and Calculated β Value of a Tetrahedral Zinc (II) Complex——Zn(2-NH_2py)_2Br_2

1 INTRODUCTION Coordination chemistry has been playing an important role in nonlinear optical (NLO) materi- als [1~3] in recent years. It has been found that tetrahedral or square pyramidal molecular configurations are useful for designing transparent second-harmonic generation (SHG) materials from coordination compounds[4]. It has also been reported that the pyridyl-based metal complexes can exhibit SHG effects[5]. Recently, we have successfully synthesized a new coordination compoun…     

ELECTRONIC STRUCTURE AND CHEMICAL BONDING OF BIS(TRIMETHYLSILYL)AMIDE DERIVATIVES OF LANTHANIDES(Ln(N(SiMe_3)_2)_3, Ln=Nd, Eu, Yb)

The electronic structure and chemical bonding of Ln(N(SiMe_3)_2)_3 have been studied by INDO calcula-tions. The results have shown that the Ln-N bonds are considerably covalent in character and that thecovalency decreases with increasing atomic numbers. A new explanation of the pyramidal structure of thecompounds has been proposed based on 5d orbital participation in bonding. With the calculation of asimplified model of Eu(N(SiMe_3)_2)_3. OPPh_3, the roles of electronic and steric effects in bonding have beencompared.     

Synthesis,Crystal Structure and Luminescence of One-dimensional Homochiral Terbium (Ⅲ) Coordination Polymers

Enantiomerically pure lanthanide(Ⅲ)-based phosphonates are successfully synthesized by using(R)-or(S)-(1-phenylethylamino)-methylphosphonate acid(pempH_2), namely, R-or S-[Tb_3(pempH_2)_2(pempH)_7]-Cl_2·H_2O(R-Tb or S-Tb), crystallizing in chiral space group P2_12_12_1. Compound R-Tb shows a one-dimensional homochiral triple-stranded helical chain structure where the Tb(III) atoms are bridged by O-P-O units and μ_3-O(P) bridge. The thermal analysis, photoluminescence as well as optically active properties of compounds R-Tb and S-Tb have also been investigated.     

Cyanide-bridged One-dimensional Heterobimetallic Complex cis-[Fe~Ⅱ(phen)_2(CN)_2Mn~Ⅲ(salen)](PF_6): Synthesis,Crystal Structure and Magnetic Properties

Dicyanide building block cis-Fe(phen)_2(CN)_2 and [Mn~Ⅲ(salen)](ClO_4) have been used to design and synthesize a cyanide-bridged complex, resulting in a heterobimetallic one-dimensional(1D) zigzag chain complex 1, [cis-Fe(phen)_2(CN)_2Mn(salen)](PF_6)(phen =1,10-phenanthroline, salen=N,N?-ethylenebis-(salicylideneaminato) dianion). Single-crystal X-ray diffraction analysis shows complex 1 crystallizes in the monoclinic P2_(1/c) space group and the asymmetric unit contains one [-NC-Fe(phen)_2(μ-CN)-Mn~Ⅲ-(salen)-]~+ cation and one PF_6~- anion. In the cationic structure of 1, each Fe~Ⅱ(phen)_2(CN)_2 connects two [Mn~Ⅲ(salen)]~+ with two cyanide groups in a cis-conformation, and in turn each [Mn~Ⅲ(salen)]~+ unit links two Fe~Ⅱ(phen)2(CN)_2 building blocks in a trans-conformation, resulting in a 1D [-NC-Fe~Ⅱ-CN-Mn~Ⅲ-]n chain. Furthermore, the electronic absorption spectra and electrochemical and magnetic properties of complex 1 have also been studied.     

Crystal Structure of 10-(2'''',5''''-Dimethoxybenzylidene) Anthrone

1 INTRODUCTION The 10-benzylidene anthrones which are important intermediate for organic syntheses[1～3] usually possess thermochromism[4] and photo- chromism[5], and have been found recently to have evident anti-cancer activity[6]. We found that the substituents in the phenyl ring will affect the bioactivity of those compounds. For more deeply investigating the structure-activity relationships (SAR) and understanding interactions between the three dimensional structure of the compound …     

One Novel Mn(Ⅱ) Complex with 1-Substituted-1H-1,2,3-triazole-4-carboxylic Acid:Crystal Structure,Fluorescence and Hirshfeld Surface Analysis

The crystal structure of one novel Mn(II) complex, [Mn(pmta)_3]_2[Mn(H_2O)_6]·4H_2O(1), is reported(Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid). In the title compound, the asymmetric unit consists of a [Mn(pmta_)3]ˉ anion, half [Mn(H_2O)_6]~(2+) counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.     

Theoretical Study on Enol-keto Tautomerism of α-Fluorine-β-diketones

1 INTRODUCTION β-diketones are a class of high functional com- pounds with outstanding optical, electric and magne- tic properties[1], and the negative ion may act as an excellent chelating agent. Hall[2] have studied β-di- ketone/metal ion complexes and indicated that the ability of combination correlates with the keto-enol distribution in solution. The enol-keto equilibrium existing in β-diketones has been extensively studied over several decades[3~9]. Burdett[10] have investiga- ted…     

Coordination Assemblies of Cd~(Ⅱ) with 5-(Ethylthio)-1H-tetrazole and Halide Ions: Synthesis,Structure, and Luminescent Properties

Three cadmium(II)-halide complexes with 5-(ethylthio)-1H-tetrazole(Hett) as ligand, namely [Cd_7Cl_2(ett)_(12)(H_2O)_2]_n(1), [Cd_2(OH)Br(ett)_2]_n(2) and [Cd_2(OH)I(ett)_2]_n(3), have been hydrothermally synthesized and characterized. Complex 1 was synthesized at pH = 7 and exhibits a 3D supramolecular framework, where the adjacent Cd ions form a tetrahedron unit by ett ligands bridge and the tetrahedron units share vertices to connect each other by ett bridges to form a 2D layer architecture, which is further interlinked by μ_2-Cl to form 3D structures. Complexes 2 and 3 are isostructural, generated at pH = 8.0~9.0, displaying similar 2D networks via ett ligands and different halide ions(Br-in 2, I-in 3, respectively). In addition, thermal stabilities and luminescent properties of new complexes 1~3 have been studied.     

Synthesis and Crystal Structure of cis-Bis(3-hydroxy2-ethyl-4-pyranonato)dioxomolybdenum(Ⅵ)

1 INTRODUCTION 3-Hydroxy-2-methyl-4-pyranone (maltol) and 3-hydroxy-2-ethyl-4-pyranone (ethylmaltol) are nontoxic compounds that have been applied to bio- inorganic chemistry over several decades[1, 2]. Their iron(III) complexes are relevant to the control of iron levels in the human body. Such complexes have been assessed for the amelioration of anaemia[3] and their respective ligands have been tested for the removal of excess burdens of iron in diseases such as siderosis, haemochroma…     

Synthesis,Crystal Structure and Spectroscopic Properties of Cyanide-bridged Complex [Ru~Ⅱ(ttpy)(CN)_3Mn~Ⅲ(salen)]

Tricyanide building block K[Ru(ttpy)(CN)_3] and [Mn~Ⅲ(salen)](ClO_4) have been used to design and synthesize a heterobimetallic one-dimensional(1D) zigzag chain complex 1,[Ru~Ⅱ(ttpy)(CN)_3 Mn~Ⅲ(salen)](ttpy = 4?-(p-tolyl)-2,2?:6?,2??-terpyridine, salen = N,N?-ethylenebis-(salicylideneaminato)dianion). Single-crystal X-ray diffraction analysis shows complex 1 crystallizes in orthorhombic Pbca space group and the asymmetric unit of 1 contains one[-NC-Ru~Ⅱ(ttpy)(CN)(m-CN)-Mn ~Ⅲ-(salen)-] molecule. In the structure of 1, each [Ru ~Ⅱ(ttpy)(CN)_3]~-connects two [Mn~Ⅲ(salen)]~+ with two cyanide groups in a cis-conformation, and in turn each[Mn~Ⅲ(salen)]~+ unit links two [Ru~Ⅱ(ttpy)(CN)_3]~-building blocks in a trans-conformation, resulting in a 1D [-NC-Ru~Ⅱ-CN-Mn~Ⅲ-]_n chain. Furthermore, the electronic absorption spectra and luminescence spectroscopy of complex 1 have also been studied.     

Solvothermal Syntheses of (H_2en)_2Sn_2S_6·en and[(H_2hmda)_3(Hhmda)_2](Sn_2S_6)_2Using SnCl_4 and S_8 as Starting Materials

1 INTRODUCTION Since Bedard et al. reported microporous tin(IV) sulfides synthesized by hydrothermal method in the presence of organic amine in 1989[1, 2], a number of thiostannates have been synthesized using hydro- or solvothermal techniques with organic amines as tem- plates. The structures of the resulting tin(IV) sulfi- des are related to the types of organic amines. Two- dimensional polyanions of the types of [Sn3S7]2- and [Sn4S9]2-, which are denoted as SnS-1 and SnS-3, respe…     

Syntheses and Structures of Two Ruthenium(III)Complexes [Ru(PPh_3)_2(S_2CNR_2)Cl_2]·CH_2Cl_2(R=Et and ~iPr)

Oxidation reaction of [Ru(PPh_3)_3Cl_2] with tetraethylthiuram disulfide[Et_2NCS_2]_2 or tetra-iso-pmpylthiumm disulfide[~iPr_2NCS_2]_2 afforded mthenium(Ⅲ)complexes[Ru(PPh_3)_2(S_2CNR_2)cl_2]·CH2Cl2(R=Et 1,~iPr 2)which were characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group Pīwith a=11.5065(6),b=12.1458(7),C=18.0034(9)(A),α=109.380(4),β=95.279(4),γ=97.969(4)°,ν=2324.8(2)(A)~3 and Z=2.Complex 2 belongs to the monoclinic system,space group P21/n with a=12.5752(3),b=20.7562(5),e=17.6821(3)(A),β=105.934(1)°,ν=4437.94(17)(A)~3 and Z=4.Both mononuclear complexes 1 and 2 have an octahedral configuration around the central ruthenium atom which is bonded to one chelated dithiocarbamate ligand,two PPh_3 ligands in mutually tram and two chlorides in mutually cis positions.The average Ru-S,Ru-P and Ru-Cl bond lengths are 2.377(2),2.412(2)and 2.369(2)(A) for 1,and 2.376(2),2.414(1)and 2.383(2)(A) for 2,respectively.The electrochemical properties of these two complexes were studied in CH_2Cl_2 solution by cyclic voltammetry.     

Synthesis,Crystal Structure and Spectroscopy Studies on Complex cis-Os~Ⅱ(bpy)_2Cl_2 and Its Oxidation Product [cis-Os~Ⅲ(bpy)_2Cl_2](PF_6)

The treatment of(NH_4)_2 OsCl_6 with 2 equiv of bpy in ethylene glycol produced complex 1, cis-Os~Ⅱ(bpy)_2Cl_2(bpy = 2,2?-bipyridine). Its one-electron oxidation product 2, [cis-Os~Ⅲ-(bpy)_2Cl_2](PF_6), was obtained by the oxidation of 1 with(Cp)_2 FePF_6. Complex 1 crystallizes in the orthorhombic space group Pbca, and adopts distorted [MCl_2 N_4] octahedral coordination, in which four coordination sites are occupied by four nitrogen atoms from two bpy ligands and the other two sites are occupied by two chlorine atoms in a cis-position. Complex 2 crystallizes in monoclinic space group C2/c, and contains one [Os(bpy)_2Cl_2]~+ cation, one PF_6~- anion and two uncoordinated water solvent molecules.     

Syntheses,Structures and Properties of Two Mn(Ⅱ) Clusters Based on 1,10-Phenanthroline-2,9-dicarbaldehyde Dioxime Ligand

Two novel clusters [Mn~Ⅲ_3(μ_3-O)(phendox)3]X·13H_2O(X = Cl(1), Br(2]) have been obtained from the solvothermal reactions of 1,10-phenanthroline-2,9-dicarbaldehyde dioxime(H_2phendox) with MnCl_2·4H_2O or anhydrous MnBr_2, and their structures were characterized by elemental analysis, FT-IR, XRD, TGA, MS and single-crystal X-ray diffraction. It crystallizes in trigonal, space group P3_1/c. X-ray analysis reveals that the neighbouring [Mn_3(μ_3-O)(phendox)_3]+ cores are linked by C–H···Cl hydrogen bonds and form an infinite supramolecular chain along the c-axis. Neighbouring chains are packed with each other by off-set p-p interactions of the aromatic rings on phenox2-. A 3D supramolecular architecture in a honeycomb topology is formed with 1D hexagonal channel in the dimensions of 13? × 13? along the c-axis. The gas adsorption studies show that compound 1·13H_2O is stable upon the removal of guest molecules and the desolvated compound absorbed considerable amount of CO_2.     

Two Coordination Polymers Constructed by Cd(Ⅱ) and Zn(Ⅱ) with in situ Generated 5-(3-Pyridyl)tetrazolate Ligand:Syntheses,Crystal Structures and Luminescence Properties

Hydrothermal reactions of 3-cyanopyridine and Na N3 with Zn Cl_2 or Cd Cl_2·5/2H_2 O in the presence of 1,4-benzenedicarboxylic acid(H2bdc) yielded two new coordination polymers,{[Zn(3-ptz)(bdc)_(0.5)(H_2O)_2]n·2H_2O}_n(1) and [Cd_2(3-ptz)_2Cl_2]_n(2),based on in situ synthesized 5-(3-pyridyl)tetrazolate(3-ptz-) organic ligand.They have been structurally characterized by elemental analysis(EA),infrared spectroscopy(IR) and single-crystal/powder X-ray diffraction(PXRD).In 1,two Zn(Ⅱ) ions are linked together through two μ_2-(3-ptz-) ligands to form a dimeric unit of [Zn(μ_2-3-ptz)(H_2O)_2]_2~(2+),which is further connected with other equivalent units by μ_2-bdc~(2-)spacers,resulting in an infinite 1D polymeric chain of [Zn_2(3-ptz)_2(H_2O)_2(bdc)]_n,and then strong hydrogen bonding interactions extend these 1D chains into a 3D supramolecular structure.In 2,the Cd(Ⅱ) ions are connected through μ_4-(3-ptz-) ligands and Cl-anions,leading to infinite 2D layers of [Cd_2(3-ptz)Cl_2]_n~(n+),which are further linked by another μ_4-(3-ptz-) pillared ligand to form a 3D layered-pillared framework architecture of [Cd)2(3-ptz))2Cl)2])n.Furthermore,thermal stability of these compounds was measured by thermogravimetric analysis(TGA) and their photoluminescent properties were also investigated in the solid state at room temperature.     

Synthesis and Structural Study of a N-Heterocyclic Carbene Trinuclear Silver(Ⅰ) Complex

The bis-benzimidazolium salt bis[2-(N-ethylbenzimidazoliumyl)ethyl]amine hexafluorophosphate(LH_2·(PF_6)_2) and its N-heterocyclic carbene silver(Ⅰ) complex[L_2Ag_3](PF_6)_3(1)have been prepared and characterized.In complex 1,a trinuclear silver(Ⅰ) architecture is formed by two tridentate ligands and three silver(I) atoms,in which one 12- and two 7-membered rings are contained.In the crystal packing of 1,1D chain and 2D supramolecular layer are formed via intermolecular weak interactions,including π…π interactions and C-H…π contacts.Additionally,the fluorescence emission spectra of LH_2-(PF_6)2 and 1 are described.     

Size Dependence of Electronic Excitation Energy in Linear C_(2n)H and C_(2n-1)N

IntroductionCarbon chains are among the most attractivecandidates as the carriers of the diffuse interstellarbands ( DIBs) [1] .To detect the carbon chains indark clouds and carbon stars[2 ] ,itis very importantto understand their electronic spectra.Maier andhis coworkers have measured the polyacetylenicradicals C2 n H( n=1— 4) and C2 n-1H( n=2— 6) bythe rotational spectroscopy[3 ,4] and the species n≤ 4have been detected in dark interstellar clouds[5,6] .In neon matrices,the B2 Π← X2…