The Reactions of Two New Alkoxy-silyl Functionalized Alkynes with M<Subscript>3</Subscript>(CO)<Subscript>12</Subscript> {M = Fe,Ru} and Co<Subscript>2</Subscript>(CO)<Subscript>8</Subscript>. Spectroscopic Identification of the Products

The new alkoxysilyl-functionalized alkynes [HC≡CCH₂N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] and [HC≡C(C₆H₄)–N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] have been synthesized using literature methods. These have been reacted with Fe₃(CO)₁₂, Ru₃(CO)₁₂ and Co₂(CO)₈. With the iron carbonyl only decomposition was observed: with Ru₃(CO)₁₂ splitting of the alkynes into their parent components and formation of the complexes (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃], (μ-H)Ru₃(CO)₉[C–C(C₆H₄)NH₂] and (μ-H)₂Ru₃(CO)₉[HC–CCH₃] occurred. Finally, with Co₂(CO)₈ formation of complexes Co₂(CO)₆(HC₂R) R=(C₆H₄)NH₂, CH₂NH(CO)NH(CH₂)₃Si(OEt)₃, (C₆H₄)NH(CO)NH(CH₂)₃Si(OEt)₃ containing the intact alkynes could be obtained.     

Spectrophotometric Studies of the Thermodynamics of Molecular Complexation between Free Base Meso-Tetraarylporphyrins and Iodine(III) Chloride

A spectrophotometric method was used for the molecular complexation of ICl₃ with para-substituted meso-tetraarylporphyrins (H₂t(4-X)pp; X: OCH₃, CH(CH₃)₂, CH₃, H and Cl) in methanol/chloroform (2.5% v/v) solution. The equilibrium constants and the thermodynamic parameters were measured spectrophotometrically at various temperatures for 1:1 molecular complex formation of meso-tetraarylporphyrins as electron donors with ICl₃ as the electron acceptor. The formation constants for the molecular complexes change according to the following trend: [ICl₃(H₂t(4-OCH₃)pp)]>[ICl₃(H₂t(4-CH(CH₃)₂)pp)]>[ICl₃(H₂t(4-CH₃)pp)]>[ICl₃(H₂tpp)]>([ICl₃(H₂t(4-Cl)pp)]. Further, the thermodynamic parameters, ΔG ^o,ΔH ^o and ΔS ^o, for formation of the complexes were obtained.     

Acetate-Functionalized Zirconium-Substituted Tungstogermanate, [Zr4O2(OH)2(CH3COO)2(α-GeW10O37)2]12−

The two acetate-functionalized zirconium(IV)-substituted tungstogermanates, Na₈K₄[Zr₄O₂(OH)₂(CH₃COO)₂(α-GeW₁₀O₃₇)₂] · 33H₂O and Na₈Cs₄[Zr₄O₂(OH)₂(CH₃COO)₂(α-GeW₁₀O₃₇)₂] · 32H₂O, were synthesized by the reaction of ZrOCl₂ with [A-α-GeW₉O₃₄]¹⁰⁻ in pH = 4.8 buffer and their structures were determined by single-crystal X-ray analysis. Both of them contain a centrosymmetric polyanion [Zr₄O₂(OH)₂(CH₃COO)₂(α-GeW₁₀O₃₇)₂]¹²⁻ consisting of two {α-GeW₁₀O₃₇} units sandwiching an inorganic–organic hybrid {Zr₄O₂(OH)₂(CH₃COO)₂} cluster. The polyanion contains a mixing of seven- and eight-coordinate Zr centres. The two compounds were also characterized by elemental analysis, IR spectroscopy, UV–vis and TG–DSC analysis.     

Acid-Base Interactions of Pyrazine,Ethyl Acetate,Di-alcohols,and Lysine with the cyclic Alumosiloxane (Ph2SiO)8[Al(O)OH]4 in View of Mimicking Al2O3(H2O) Surface Reactions

The etherate of (Ph₂SiO)₈[Al(O)OH]₄ can be transformed into the pyrazine adduct (Ph₂SiO)₈[Al(O)OH]₄ · 3N(C₂H₂)₂N ( 1 ), the ethyl acetate adduct (Ph₂SiO)₈[Al(O)OH]₄ · 3H₃C-C(O)OC₂H₅ ( 2 ), the 1,6-hexane diol adduct (Ph₂SiO)₈[Al(O)OH]₄ · 2HO–CH₂(CH₂)₄CH₂–OH ( 3 ) and the 1,4-cyclohexane diol adduct (Ph₂SiO)₈[Al(O)OH]₄ · 4HO–CH(CH₂CH₂)₂CH–OH ( 4 ). In all compounds the OH groups of the starting material bind to the bases through O–H ··· N ( 1 ) or O–H ··· O hydrogen bonds ( 2 , 3 , 4 ) as found from single-crystal X-ray diffraction analyses. Whereas in 1 only three of the central OH groups bind to the pyrazines, in 2 two of them bind to the same carbonyl oxygen atom of the ethyl acetate resulting in an unprecedented O–H ··· O ··· H–O double hydrogen bridge. The hexane diol adduct 3 in the crystal forms a one-dimensional coordination polymer with an intramolecularly to two OH groups grafted hexane diol loop, while the second hexane diol is connecting intermolecularly. In the cyclohexane diol adduct 4 all OH groups of the central Al₄(OH)₄ ring bind to different diols, leaving one alcohol group per diol uncoordinated. These “free” OH groups form an (O-H ··· )₄ assembly creating a three-dimensional overall structure. When reacting with (Ph₂SiO)₈[Al(O)OH]₄ lysine loses water, turns into the cyclic 3-amino-2-azepanone, and transforms through chelation of one of the aluminum atoms the starting material into a new polycycle. The isolated compound has the composition (Ph₂SiO)₁₂[Al(O)OH]₄[Al₂O₃]₂ · 4 C₆H₁₂N₂O · 6(CH₂)₄O ( 5 ).     

[2,6(9)-B10H8>(O)2CCH3]− and [2,7(8)-B10H8(OC(O)CH3)2]2− derivatives in synthesis of position isomers of the [B10H8(OC(O)CH3)(OH)]2− anion with the 2,6(9)- and 2,7(8)-arrangement of functional groups

The interaction of Cat₂B₁₀H₁₀ (Cat = Ph₄P⁺, Ph₄As⁺) with acetic acid has been studied. Disubstituted closo-decaborate derivatives with a bidentately bound acetate group, Cat[2,6(9)-B₁₀H₈>(O)₂CCH₃], or two monodentate acetate groups, Cat₂[2,7(8)-B₁₀H₈(OC(O)CH₃)₂], have been isolated (Cat = Ph₄P⁺, Ph₄As⁺). Hydrolysis of these compounds has led to the position isomers of the [B₁₀H₈(OC(O)CH₃)(OH)]^2? anion with the hydroxo and acetate groups in the 2,6(9)- and 2,7(8)-positions. The structures of {Pb(Bipy)₂[2,6(9)-B₁₀H₈(OC(O)CH₃)(OH)]}₂ · 3H₂O, (Ph₄As)₂[2,6(9)-B₁₀H₈(OC(O)CH₃)(OH)] · 0.4C₂H₅OH · 0.25H₂O, and (Ph₄As)₂[2,7(8)-B₁₀H₈(OC(O)CH₃)(OH)], as well as of the product of the reaction of the B₁₀H ₁₀ ^2? anion with formic acid (Ph₄P)₂[2-B₁₀H₉OC(O)H] · CH₃CN, have been determined by X-ray crystallography.     

Thermal Studies of N-phenylethane-1,2-diamine Complexes of Nickel(II) in the Solid State

[NiL₃]X₂ (where L=N-phenylethane-1,2-diamine and X=I⁻ and ClO₄ ⁻), [NiL₂X₂] (X is Cl⁻, Br⁻, NCS⁻, 0.5SO₄ ²⁻ or 0.5SeO₄ ²⁻) and [NiL₂(H₂O)₂](NO₃)₂ have been synthesized from solution and their thermal study has been carried out in the solid phase. [NiL₂Cl₂] upon heating undergoes irreversible endothermic phase transition (142–152°C, ΔH=0.35 kJ mol⁻¹) without showing any visual colour change. This phase transition is assumed to be due to conformation changes of the diamine chelate rings. NiLCl₂ and NiL_2.5I₂ have been prepared pyrolytically from [NiL₂Cl₂] and [NiL₃]I₂ respectively in the solid state. [NiL₂(H₂O)₂](NO₃)₂ upon heating undergoes deaquation-anation reaction without showing any visual colour change. [NiL₂X₂] (X is Cl⁻, Br⁻, NCS⁻), [NiL₂(H₂O)₂](NO₃)₂ and [NiL₂(NO₃)₂] possess trans-octahedral configuration, whereas, [NiL₂X₂] (X is 0.5SO₄ ²⁻ or 0.5SeO₄ ²⁻) are having cis-octahedral configuration. Amongst the complexes, only NiLCl₂ shows unusually high (5.1 BM at 27°C) magnetic susceptibility value. This revised version was published online in July 2006 with corrections to the Cover Date.     

Self-assembly of reduced molybdophosphate-based supramolecular architectures and the study of their magnetic properties

Reduced molybdophosphate-based supramolecular compounds, such as (4,4′-H₂bipy)[Co(H₂O)₂]₂[Co(H₂PO₄)₂(HPO₄)₄(PO₄)₂(MoO₂)₁₂(OH)₆] · 17H₂O (1), [Co(2,2′-bipy)₂(H₂O)]₄[Co(H₂O)₂][Co(HPO₄)₆(PO₄)₂(MoO₂)₁₂(OH)₆] · 2H₂O (2), and [Co(2,2′-bipy)₂(H₂O)]₄[Co(H₂PO₄)(H₂O)₂]₂[Co(HPO₄)₆(PO₄)₂(MoO₂)₁₂(OH)₆] · 8H₂O (3) (4,4′-bipy=4,4′-bipyridine, 2,2′-bipy=2,2′-bipyridine), have been synthesized under hydrothermal conditions and characterized. Compound 1 exhibits a three-dimensional supramolecular twofold interpenetrating architecture built up of one-dimensional [P₄Mo₆]-based infinite covalent chains and free 4,4′-bipy molecules. Compound 2 also shows a three-dimensional supramolecular network constructed from one-dimensional covalent [P₄Mo₆]-based chains. Unlike compounds 1 and 2, compound 3 exhibits an interesting three-dimensional ‘honeycomb-like’ supramolecular network constructed by the stacking of [Co(2,2′-bipy)₂(H₂O)] units with one-dimensional channels, in which the [P₄Mo₆]-based polyoxometalate chains are located. The magnetic properties of compounds 2 and 3 are reported. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Reactions of Ru3(CO)12 with Ene-yne and Alkoxy-silyl Functionalized Compounds. The Crystal Structure of (μ-H)Ru3(CO)9[μ3-η2-HC=N(CH2)3Si(OEt)3]

Ru₃(CO)₁₂ has been reacted with the compounds hex-1-en-3-yne [EtC≡CCH=CH₂], 2-methyl-hex-1-en-3-yne [EtC≡CC(=CH₂)CH₃] and with 3(ethoxy-silyl)propyl isocyanate [(EtO)₃Si(CH₂)₃NCO] and the compound tb [(EtO)₃Si(CH₂)₃NHC(=O)OCH₂C≡CCH₂OC(=O)NH(CH₂)₃Si(OEt)₃] in hydrocarbon solution. Some reactions in CH₃OH/KOH solution (followed by acidification) have also been performed. The main products of the reactions with ene-ynes are the clusters Ru₃(CO)₆(μ-CO)₂L₂ (L = C₆H₈, C₇H₁₀) and their demolition products, the “ferrole” Ru₂(CO)₆L₂ complexes. One of the isomers of Ru₃(CO)₆(μ-CO)₂L₂, and Ru₂(CO)₆L₂ (L = C₇H₁₀) have been reacted with vinyl-triethoxysilane [(EtO)₃SiCH=CH₂]: these reactions did not afford complexes containing new carbon–carbon bonds or triethoxy-silyl groups. Only polymerization of vinyl-triethoxysilane occurred. The reactions of Ru₃(CO)₁₂ with triethoxysilyl-propyl-isocyanate and tb (in the presence of Me₃NO) lead to the same products, that is the isomeric complexes (μ-H)Ru₃(CO)₉[C=N(H)(CH₂)₃Si(OEt)₃] with a “perpendicular” ligand (complex 3, as proposed on the basis of spectroscopic results) and (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃] with a “parallel” ligand (complex 4, as confirmed by a X-ray analysis). The reaction pathways leading to these products are discussed. Complex 4 has been reacted with tetraethyl orthosilicate and the resulting material has been characterized. These reactions are part of a study on the synthesis of inorganic-organometallic materials through sol–gel techniques. This paper is dedicated to Prof. Gunther Schmid in the occasion of his 70th birthday.     

1,2-环己二胺缩邻香兰素单核与四核镱稀土配合物的近红外性质

通过配体1,2-环己二胺缩邻香兰素（H₂L）和不同的镱盐反应,合成了4个镱稀土配合物[Yb（H₂L）₂]（ClO₄）₃·2CH₃OH·H₂O（1）,[Yb₄（L）₄（NO₃）₂（H₂O）₂]（PF₆）₂·4CH₃CN（2）,[Yb₄（L）₄（H₂O）₂Cl₂]（PF₆）₂·2CH₂Cl₂·2H₂O（3）和[Yb₄（L）₄（NO₃）₂（H₂O）₂][Yb（NO₃）₃（H₂O）₂（CH₃OH）]（NO₃）₂ ·4CH₂Cl₂·6CH₃OH（4）。X射线单晶衍射分析表明配合物1为零维的单核结构,配合物2~4均为四核结构。研究了4个配合物的近红外发光性能。     

Synthesis and properties of pentamethylmetallocene derivatives Cp*MCp (M = Ru, Fe). Crystal structure of the salt [CpRuC5Me4CH2+OC6H2(NO2)3-]

Photolysis of a solution of Cp*RuCp (1) in CF₃CO₂H generates salt [CpRu(C₅Me₄CH₂)]-(O₂CCF₃)(2 • O₂CCF₃). The reaction of compound 1 with oleum at 20 °C through the intermediate dication [η⁵-(CH₂C₅Me₄)Ru(μ:η⁵,ν⁵-C₅H₄C₅H₅)Ru(C₅Me₄CH₂)-η⁶]²⁺ leads to the triply charged cation η⁷CH₂)₂C₅Me₃Ru(μη⁵,η⁵-C₅H₄C₅H₄)Ru(C₅Me₄CH₂)-η⁶]³⁺. Synthesis of pentamethylmetallocene derivatives CpMC₅Me₄X (M = Ru, Fe; X = CHO, CH₂OH, CH₂An) has been accomplished. The reactions of 1-hydroxymethyl-2,3,4,5-tetramethylruthenocene with acids CF₃CO₂H, HBF₄, CF₃CO₂H/NaB[C₆H₃(CF₃)₂]₄, and picric acid C₆H₂(NO₂)₃OH afforded salts 2•X (X = CF₃CO₂, BF₄, B[C₆H₃(CF₃)₂]₄), and (2,3,4,5-tetram ethylruthenocenyl)methyl picrate [CpRu(C₅Me₄CH₂)-η⁶][(C₆H₂(NO₂)₃O] (2•C₆H₂(NO₂)₃O). Structure of the latter was characterized by single crystal X-ray diffraction.     

Synthesis, crystal structure and forming mechanism of two novel copper (II) α-methacrylate complexes with benzimidazole

Two copper (II) α-Methacrylate complexes with benzimidazole, Cu[CH₂ = C(CH₃)-COO]₂ (C₃H₆N₂)₂(1) and Cu₂[CH₂ = C(CH₁)-COO]₂(C₃H₆N₂)₂(2), have been prepared and characterized by elemental analyses, IR and electronic reflectance spectroscopies. ’The single crystal X-ray diffraction study of the two complexes shows that complex 1 has a square planar configuration, while complex 2 has a binuclear cage structure. The crystal structural analyses show that both complexes 1 and 2 are monoclinic. with space group p2₁/c,a = 0.924 16(8) nm,b = 1.233 02(13) nm,c = 0.989 1(3) nm,β = 91.912 (13),D _c = 1.386 g/cm³,Z=2,R = 0.033 9 for the former; anda = 0.905 7(2) nm,b = 2.252 1(5) nm,c = 1.623 5(4) nm,β = 90.11 (2),D _c = 1.411 g/cm³,Z = 4,R = 0.056 8, Cu-Cu = 0.266 21 nm for tin latter. Different structural types of complexes 1 and 2 were produced simultaneously in the reaction of copper (II) α-methacrylate with benzimidazole in methanol solution. ’The forming mechanism of the complexes has been summanzed. Project supported by the national natural Science Foundation of China (Grant No. 29831010) and the Foundation of the State Key Laboratory of Coordination Chemistry of Nanjing university.     

Synthesis,characterization and structure of the Bis(methyl-cyclopentadienyl)vanadium(IV) carboxylates

The 1,1’-dimethylvanadocene dichloride ((C₅H₄CH₃)₂VCl₂) reacts in aqueous solution with various carboxylic acids giving two different types of complexes. The 1,1’-dimethylvanadocene complexes of monocarboxylic acids (C₅H₄CH₃)₂V(OOCR)₂ (R=H,CCl₃, CF₃, C₆H₅) contain two monodentate carboxylic ligands, whereas oxalic and malonic acids act as chelate compounds of the formula (C₅H₄CH₃)₂V(OOC-A-COO) (A=−, CH₂). The structure of the (C₅H₄CH₃)₂ V(OOCCF₃)₂ complex was determined by single crystal X-ray diffraction analysis. The isotropic and anisotropic EPR spectra of all the complexes prepared were recorded. The obtained EPR parameter values were found to be in agreement with proposed structures.     

γ-Hydroxypropyl-functionalised iron thiolate complexes: crystal and molecular structure of [{Fe2(CO)6(μ-SCH2CH2CH2OH)}2(μ4-S)]

The γ-hydroxypropyl-functionalised diiron dithiolate complex [Fe₂(CO)₆(μ-SCH₂CH₂CH₂OH)₂] is prepared upon thermolysis of Fe₃(CO)₁₂ and HO(CH₂)₃SH and further reaction with dppm (dppm = Ph₂PCH₂PPh₂) affords [Fe₂(CO)₄(μ-dppm)(μ-SCH₂CH₂CH₂OH)₂]. From the reaction of Fe₃(CO)₁₂ with dppm(S₂) a minor product is the tetrairon cluster, [{Fe₂(CO)₆(μ-SCH₂CH₂CH₂OH)}₂(μ⁴-S)], the mode of formation of which is unclear. It has been crystallographically characterised and adopts a μ⁴-S bridged double butterfly structure which is compared with other crystallographically characterised complexes of this type. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Reactivity of Mo3PdS4+ 4 Cluster: Evidence for New Ligands PhP(OH)2 and Ph2P(OH) and Structural Characterization of [Mo3(Pd(PPh3))S4(H2O)5Cl4]⋅0.5CH3OH⋅3H2O

Cuboidal cluster aqua complex [Mo₃(PdCl)S₄(H₂O)₉]³⁺ in 4M HCl causes isomerization of (HO)₂P(O)(H), (HO)P(O)(H)₂, PhP(O)(OH)(H), and Ph₂P(O)(H) into hydroxo tautomers P(OH)₃, HP(OH)₂, PhP(OH)₂, and Ph₂P(OH) which are stabilized by P coordination to the Pd atom in the cluster. The reactions were followed by ³¹P NMR and UV/Vis spectroscopy. Hypophosphorous acid H₂P(O)(OH) in the presence of the cluster is rapidly oxidized into phosphorous acid; the reaction can be made catalytic. Coordination of PPh₃ also takes place, giving [Mo₃(Pd(PPh₃))S₄(H₂O)₅Cl₄]0.5CH₃OH3H₂O, whose crystal structure was determined.     

Low-Dimensional Architectures in Isomeric cis-PtCl2{Ph2PCH2N(Ar)CH2PPh2} Complexes Using Regioselective-N(Aryl)-Group Manipulation

The solid-state behaviour of two series of isomeric, phenol-substituted, aminomethylphosphines, as the free ligands and bound to Pt^II, have been extensively studied using single crystal X-ray crystallography. In the first library, isomeric diphosphines of the type Ph₂PCH₂N(Ar)CH₂PPh₂ [1a–e; Ar = C₆H₃(Me)(OH)] and, in the second library, amide-functionalised, isomeric ligands Ph₂PCH₂N{CH₂C(O)NH(Ar)}CH₂PPh₂ [2a–e; Ar = C₆H₃(Me)(OH)], were synthesised by reaction of Ph₂PCH₂OH and the appropriate amine in CH₃OH, and isolated as colourless solids or oils in good yield. The non-methyl, substituted diphosphines Ph₂PCH₂N{CH₂C(O)NH(Ar)}CH₂PPh₂ [2f, Ar = 3-C₆H₄(OH); 2g, Ar = 4-C₆H₄(OH)] and Ph₂PCH₂N(Ar)CH₂PPh₂ [3, Ar = 3-C₆H₄(OH)] were also prepared for comparative purposes. Reactions of 1a–e, 2a–g, or 3 with PtCl₂(η⁴-cod) afforded the corresponding square-planar complexes 4a–e, 5a–g, and 6 in good to high isolated yields. All new compounds were characterised using a range of spectroscopic (¹H, ³¹P{¹H}, FT–IR) and analytical techniques. Single crystal X-ray structures have been determined for 1a, 1b∙CH₃OH, 2f∙CH₃OH, 2g, 3, 4b∙(CH₃)₂SO, 4c∙CHCl₃, 4d∙½Et₂O, 4e∙½CHCl₃∙½CH₃OH, 5a∙½Et₂O, 5b, 5c∙¼H₂O, 5d∙Et₂O, and 6∙(CH₃)₂SO. The free phenolic group in 1b∙CH₃OH, 2f∙CH₃OH_, 2g, 4b∙(CH₃)₂SO, 5a∙½Et₂O, 5c∙¼H₂O, and 6∙(CH₃)₂SO exhibits various intra- or intermolecular O–H∙∙∙X (X = O, N, P, Cl) hydrogen contacts leading to different packing arrangements.     

1，2-环己二胺缩邻香兰素单核与四核镱稀土配合物的近红外性质

通过配体1,2-环己二胺缩邻香兰素（H2L）和不同的镱盐反应,合成了4个镱稀土配合物[Yb（H₂L）₂]（ClO₄）₃·2CH₃OH·H₂O（1）,[Yb₄（L）₄（NO₃）₂（H₂O）₂]（PF₆）₂·4CH₃CN（2）,[Yb₄（L）₄（H₂O）₂Cl2]（PF₆）₂·2CH₂Cl₂·2H₂O（3）和[Yb₄（L）₄（NO₃）₂（H₂O）₂][Yb（NO₃）₃（H₂O）₂（CH₃OH）]（NO₃）₂·4CH₂Cl₂·6CH₃OH（4）。X射线单晶衍射分析表明配合物1为零维的单核结构,配合物2~4均为四核结构。研究了4个配合物的近红外发光性能。     

Syntheses and structural characterization of inifinite coordination polymers from bipyridyl ligands and zinc salts

The reaction of ZnSiF₆·6H₂O with 4,4′-dipyridyldisulfide (4-PDS) in CH₃OH afforded the complex [Zn(4-PDS)₂(SiF₆)·3CH₃OH] _n , 1, while the reaction of Zn(ClO₄)₂·6H₂O with l,2-bis(4-pyridyl)ethane (bpa) in CH₃OH gave the complex [Zn(bpa)₂(ClO₄)₂·CH₃OH] _n , 2. The 4-DPS ligand in 1 is coordinated to the metal centers through both nitrogen atoms to form a 3-D open channel and the distorted octahedral coordination geometry at each zinc center is completed by a pair of trans-F-bonded hexafluorosilicate molecule. Compound 2, the channel-type 1-D chains are interlinked through C–H···O interaction to form 3-D structure with large cavities that are occupied by the methanol molecules.     

对乙酰氨基苯甲酸和含氮配体构筑铜、锌配合物的合成、结构及性质研究

利用对乙酰氨基苯甲酸（HPABA）和邻菲咯啉（phen）、硝酸铜在DMF/CH₃OH/H₂O溶液中合成了单核铜配合物[Cu（PABA）（phen）（H₂O）₂]·（NO₃）·H₂O（1）,然后又和4,4’-联吡啶（4,4’-bpy）、硝酸锌在DMF/CH₃OH/H₂O溶液中获得配位聚合物{[Zn（PABA）₂（4,4’-bpy）]·4H₂O}_n（2）。根据X射线衍射分析结果,配合物1中每个铜离子周围有2个氮原子和3个氧原子与之配位形成畸变的四方锥配位构型,然而在配合物2中,六配位八面体构型的锌离子通过配体4,4’-联吡啶扩展为一维Zigzag型链。分别对这两个配合物的热稳定性和电化学性质进行了研究。     

Syntheses,characterization and crystal structures of two square-planar Ni(II) complexes with unsymmetrical tridentate Schiff base ligands and monodentate pseudohalides

Two new square-planar Ni(II) complexes, [NiL¹(NCS)] (1) and [NiL²(N₃)] (2) have been synthesized with the unsymmetrical tridentate Schiff base ligands [(CH₃)₂NCH₂CH₂N=C(CH₃)CH=C(OH)(C₆H₅)], L ¹ H, derived from benzoylacetone and 2-dimethylaminoethylamine and [(CH₃CH₂)₂NCH₂CH₂N=C(CH₃)CH=C(OH)(C₆H₅)], L ² H, derived from benzoylacetone and 2-diethylaminoethylamine, respectively. The complexes have been characterized by elemental analysis, FT-IR, UV-Vis spectroscopy, electrochemical and thermal methods (where applicable). Structures have been established by the single-crystal X-ray diffraction technique which reveals the discrete nature of the complexes in which the metal centers adopt a distorted square planar geometry. Coordination environments of the metal ions in the complexes are satisfied with two different unsymmetrical Schiff base ligands having similar N₂O donor sets and a terminal pseudohalide anion (thiocyanate for 1 and azide for 2).     

Syntheses, Structure Characterizations and Fluorescent Properties of Two Reduced Molybdenum (V) Phosphates Functionalized by Zinc Coordination Complexes

Two new materials built from reduced molybdenum (V) phosphates as building blocks and zinc coordination complexes as linkers, (H₃O)₂[Zn(2,2′-bpy)]₄[Zn(H₂O)]₂[Zn(HPO₄)₂ (PO₄)₆(MoO₂)₁₂(OH)₆] · 6H₂O (2,2′-bpy=2,2′-bpyridine) 1 and [Zn(phen)(H₂O)₂]₂[Zn(phen) (H₂O)]₂[Zn(H₂O)]₂[Zn(HPO₄)₄ (PO₄)₄(MoO₂)₁₂ (OH)₆] · 7H₂O (phen=1,10-phenanthroline) 2, have been synthesized and characterized by elemental analyses, IR, TG, and single crystal X-ray diffraction. Compound 1 is a new 3-D structure which constructed from Zn[P₄Mo₆]₂ dimers bonded together with [Zn(2,2′-bpy)] coordination complexes and [Zn(H₂O)] fragments. In compound 2, the Zn[P₄Mo₆]₂ dimeric units are linked by [Zn(phen)(H₂O)] coordination complexes and [Zn(H₂O)] fragments to form a new 2-D framework. The fluorescent activities of compounds 1 and 2 were reported. The crystal data for the two compounds are the following: 1, triclinic, P−1, a=13.036(3) ?, b=13.765(3) ?, c=14.459(3) ?, , Z=1; 2, triclinic, P−1, a=12.708(3) ?, b=14.016(3) ?, c=14.646(3) ?, , Z=1.Dedicated to Professor Michael T. Pope on the occasion of his retirement.