Fe(Ⅲ)[TP(o-NO2)TBP]Cl与抗坏血酸的均相电子转移反应动力学

研究了在 (2 6± 0 .2 )℃、以含微量水的 DMF为溶剂、离子强度 0 .1(Na Cl O4)条件下 ,氯化四 (邻 -硝基苯基 )四苯并卟啉合铁 ( ) (Fe( ) [TP(o- NO2 ) TBP]Cl)与抗坏血酸 (H2 A)的电子转移反应动力学 ,提出了反应的机理 ,推导了反应的动力学方程为 :d[Fe( ) [TP(o- NO2 ) TBP]Cl]/ dt=k Ka1 Ka2 / ([H ]2 Ka1 [H ] Ka1 Ka2 )·[H2 A]T· [Fe( ) [TP(o- NO2 ) TBP]Cl],其中 ,k=1.90 3× 10 2 mol- 1 · L· s- 1 ,Ka1 =5 .137× 10 - 6 ,Ka2 =1.5 92× 10 - 1 2 .Ka1 、Ka2 可视为用动力学方法测出的抗坏血酸在 DMF溶液中的离解常数 .     

以N, N’-二异丁基-2, 3-二胺基喹喔啉为配体的钴和锌配合物的合成、晶体结构以及性质研究

本文以2,3-二氯喹喔啉和异丁胺为原料,合成了N,N’-二异丁基-2,3二胺基喹喔啉（L）,并合成了两个标题配合物（[Co（DIDAQX）Cl₂]）（1,DIDAQX=N,N’-Diisobutyl-2,3-（1H,4H）-diaminoquinoxaline）和（[Zn（DIDAQX）Cl₂]）（2）。并对其进行了红外、元素分析、单晶衍射、热重、荧光、电化学性质等性质研究。且对1做了密度泛函理论（DFT）计算。单晶结构分析表明1和2同构,都属于正交晶系,Pbca空间群,1的晶胞参数：a=1.4082（3）nm,b=1.4628（3）nm,c=1.7970（4）nm;V=3.7017（14）nm³,Z=8。2的晶胞参数：a=1.4082（3）nm,b=1.4648（3）nm,c=1.7969（4）nm;V=3.7065（14）nm³,Z=8。在配合物结构中每个金属原子以四配位的形式分别与2个Cl原子和来自配体的2个N原子配位,形成了一个扭曲的四面体结构。     

基于三聚硫氰酸配体的六核镍配合物的合成, 晶体结构和荧光性能分析

用缓慢挥发法合成了一个六核Ni(Ⅱ)的配位聚合物[Ni6(H2O)6(HTMT)6]·3(C2H5)3N·7H2O(1)(H3TMT=三聚硫氰酸),并用红外、元素分析及单晶衍射进行表征。该配合物属于三方晶系,R3c空间群,晶胞参数为a=b=1.869 7(3)nm,c=3.982 5(8)nm,γ=120°。晶胞体积V=12.057(4)nm3,Dc=1.596 gcm-3,Z=6,μ=1.91 mm-1,F(000)=6 095,R=0.047,wR=0.151。X单晶衍射表明,6个Ni(Ⅱ)与6个HTMT2-和6个水分子形成一个六核的构筑单元,这个六核构筑单元又通过氢键作用形成三维结构。同时在室温条件下测定了该配合物的荧光性能。     

一个二核钒配合物的合成及晶体结构：NH4[(VⅣO)2(μ2-O)(nta)2][EuⅢ(H2O)9](英)

A binuclear vanadium complex NH₄[(V^ⅣO)₂(μ₂-O)(nta)₂][Eu^Ⅲ(H₂O)₉] was synthesized by reaction of NH₃VO₃, nitrilotriacetic acid and EuCl₃ in one aqueous solution. The crystal X-ray analysis shows that the complex contains one binuclear vanadium anion [(V^ⅣO)₂(μ₂-O)(nta)2]^4- and one [Eu^Ⅲ(H₂O)₉]³⁺ cation. The molecules are built up to a three-dimensional supramolecular structure through hydrogen bonding. CCDC: 238716.     

Syntheses and Crystal Structures of (H3O)(C3H5N2)[Mn(OH)6 Mo6O18]·3.5H2O and (H3O)3[Co(OH)6Mo6O18]·7H2O

The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.     

Syntheses and Crystal Structures of Two New Supramolecular Architectures Constructed from the Main Group Metal Chloride and Protonated 2-（3-Pyridyl）benzimidazole

The reactions of SbCl3 and HgCl2 with 2-(3-pyridyl)benzimidazole (PyBIm) in solution acidified with HCl have been investigated. The PyBIm ligands are protonated into 2-(3-pyridinio)benzimidazolium (H2PyBIm) cations and the corresponding metal ions are bonded with chloride atoms into coordination anions, forming two new coordination compounds, namely, (H2PyBIm)(SbCl5) 1 and (H2PyBIm)2(Hg2Cl8) 2. Both compounds were characterized by X-ray crystallography. Crystal data for 1: triclinic, space group P1 with a = 5.7030(7), b = 9.0625(11), c = 16.5929(18) , α = 91.808(7), β = 93.234(6), γ = 99.216(7)o, C12H11N3SbCl5, Mr = 496.24, V = 844.44(17) 3, Z = 2, Dc = 1.952 g/cm3, μ(MoKα) = 2.419 mm-1, F(000) = 480, the final R = 0.0496 and wR = 0.1382 for 3433 observed reflections (I > 2σ(I)). Crystal data for 2: monoclinic, space group P21/c with a = 7.8061(5), b = 15.8127(9), c = 12.2435(9) , β = 91.955(4)o, C24H22N6Hg2Cl8, Mr = 1079.26, V = 1510.40(17) 3, Z = 2, Dc = 2.373 g/cm3, μ(MoKα) = 10.889 mm-1, F(000) = 1008, the final R = 0.0293 and wR = 0.0562 for 2854 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that the antimony(III) is five-coordinated, exhibiting a slightly distorted square-pyramidal coordination geometry; while in 2, a dimeric [Hg2Cl8]4-anion consists of two trigonal bipyramids sharing two common edges. The organic cations and coordination anions are connected into a one-dimensional belt and a two-dimensional sheet through N-H···Cl hydrogen bonding interactions in compounds 1 and 2, respectively; both are further aggregated into 3D frameworks by strong π-π contacts.     

以N,N′-二异丁基-2,3-二胺基喹喔啉为配体的钴和锌配合物的合成、晶体结构以及性质研究(英文)

以2,3-二氯喹喔啉和异丁胺为原料,合成了N,N′-二异丁基-2,3二胺基喹喔啉(L),并合成了两个标题配合物([Co(DIDAQX)Cl2])(1,DIDAQX=N,N′-Diisobutyl-2,3-(1H,4H)-diaminoquinoxaline)和([Zn(DIDAQX)Cl2])(2)。并对其进行了红外、元素分析、单晶衍射、热重、荧光、电化学性质等性质研究。且对1做了密度泛函理论(DFT)计算。单晶结构分析表明1和2同构,都属于正交晶系,Pbca空间群,1的晶胞参数:a=1.408 2(3)nm,b=1.462 8(3)nm,c=1.797 0(4)nm;V=3.701 7(14)nm3,Z=8。2的晶胞参数:a=1.408 2(3)nm,b=1.464 8(3)nm,c=1.796 9(4)nm;V=3.706 5(14)nm3,Z=8。在配合物结构中每个金属原子以四配位的形式分别与2个Cl原子和来自配体的2个N原子配位,形成了一个扭曲的四面体结构。     

基于三聚硫氰酸配体的六核镍配合物的合成,晶体结构和荧光性能分析

用缓慢挥发法合成了一个六核Ni(Ⅱ)的配位聚合物[Ni₆(H₂O)₆(HTMT)₆]·3(C₂H₅)₃N·7H₂O(1)(H₃TMT=三聚硫氰酸),并用红外、元素分析及单晶衍射进行表征。该配合物属于三方晶系,R3c空间群,晶胞参数为a=b=1.869 7(3) nm,c=3.982 5(8) nm,γ=120°。晶胞体积V=12.057(4) nm³,D_c=1.596 gcm^-3,Z=6,μ=1.91 mm-1,F(000)=6 095,R=0.047,wR=0.151。X单晶衍射表明,6个Ni(Ⅱ)与6个HTMT^2-和6个水分子形成一个六核的构筑单元,这个六核构筑单元又通过氢键作用形成三维结构。同时在室温条件下测定了该配合物的荧光性能。