混合价三核锰配合物Mn3O(O2CCCl3)6(py)2(H2O)的合成、晶体结构及磁性

A new mixed-valence trinuclear oxo-centered manganese complex Mn₃O(O₂CCCl₃)₆(py)₂(H₂O) was prepared by the reaction of NⁿBu₄MnO₄ with Mn(OAc)₂·4H₂O, trichloroacetic acid and pyridine in absolute EtOH. The crystal structure was determined. The complex crystallizes in monoclinic, space group P2₁/c, unit cell parame-ters, a=14.951(1), b=20.791(2), c=17.882(1)?,α=γ=90°, β=102.67(1)°. Variable temperature solid state magnetic susceptibility study shows that the complex has an antiferromagnetic exchange interaction. CCDC: 183369.     

Influence of Fine Ligand Substitution Modification of the Isocyanidometal Bridge on Metal-to-Metal Charge Transfer Properties in Class II–III Mixed Valence Complexes

The synthesis and characterization of Class II–III mixed valence complexes have been an interesting topic due to their special intermediate behaviour between localized and delocalized mixed valence complexes. To investigate the influence of the isocyanidometal bridge on metal-to-metal charge transfer (MMCT) properties, a family of new isocyanidometal-bridged complexes and their one-electron oxidation products cis-[Cp(dppe)Fe−CN−Ru(L)₂-NC−Fe(dppe)Cp][PF₆]_n (n=2, 3) (Cp=1,3-cyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane, L=2,2’-bipyridine (bpy, 1[PF₆]_n ), 5,5’-dimethyl-2,2’-bipyridyl (5,5’-dmbpy, 2[PF₆]_n ) and 4,4’-dimethyl-2,2’-bipyridyl (4,4’-dmbpy, 3[PF₆]_n )) have been synthesized and fully characterized. The experimental results suggest that all the one-electron oxidation products may belong to Class II–III mixed valence complexes, supported by TDDFT calculations. With the change of the substituents of the bipyridyl ligand on the Ru centre from H, 5,5’-dimethyl to 4,4’-dimethyl, the energy of MMCT for the one-electron oxidation complexes changes in the order: 1³⁺ < 2³⁺ < 3³⁺ , and that for the two-electron oxidation complexes decreases in the order 1⁴⁺ > 3⁴⁺ > 2⁴⁺ . The potential splitting (ΔE_1/2(2)) between the two terminal Fe centres for N[PF₆]₂ are the largest potential splitting for the cyanido-bridged complexes reported so far. This work shows that the smaller potential difference between the bridging and the terminal metal centres would result in the more delocalized mixed valence complex.     

Coexistence of Two Thermally Induced Intramolecular Electron Transfer Processes in a Series of Metal Complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)2] (M=Co,Fe, and Ni) bearing Non‐Innocent Catechol‐Based Ligands: A Combined Experimental and Theoretical Study

The different thermally induced intermolecular electron transfer (IET) processes that can take place in the series of complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)₂], for which M=Co ( 2 ), Fe ( 3 ) and Ni( 4 ), and Cat‐N‐BQ and Cat‐N‐SQ denote the mononegative (Cat‐N‐BQ^?) or dinegative (Cat‐N‐SQ^2?) radical forms of the tridentate Schiff‐base ligand 3,5‐di‐tert‐butyl‐1,2‐quinone‐1‐(2‐hydroxy‐3,5‐di‐tert‐butylphenyl)imine, have been studied by variable‐temperature UV/Vis and NMR spectroscopies. Depending on the metal ion, rather different behaviors are observed. Complex 2 has been found to be one of the few examples so far reported to exhibit the coexistence of two thermally induced electron transfer processes, ligand‐to‐metal (IET^LM) and ligand‐to‐ligand (IET^LL). IET^LL was only found to take place in complex 3 , and no IET was observed for complex 4 . Such experimental studies have been combined with ab initio wavefunction‐based CASSCF/CASPT2 calculations. Such a strategy allows one to solicit selectively the speculated orbitals and to access the ground states and excited‐spin states, as well as charge‐transfer states giving additional information on the different IET processes.     

混配杂多化合物[C10H10N]4PMo9W3O40·2DMF的合成、表征、晶体结构及非线性光学性质

混合价;杂多金属氧酸盐;混配杂多化合物[C10H10N]4PMo9W3O40·2DMF的合成、表征、晶体结构及非线性光学性质     

己二胺-12-钼磷酸电荷转移盐的光化学合成与晶体结构

采用光化学法合成一种有机-无机电荷转移盐,（HMDH2）[H2PMo12O40]·AA·3H2O·DMF（HMD = 1,6-己二胺,AA = 乙醛,DMF = N,N-二甲基甲酰胺）超分子化合物。用元素分析,IR,固体漫反射电子光谱,ESR进行了表征。X-射线四圆衍射测定其晶体结构属三斜晶系,空间群Pī,Mr=2081.68,晶胞参数a = 14.092(3),b =14.347(3),c =14.358(3)?,α=75.10(3),β=80.70(3),γ=80.73(3)°,V=2746.6(10)?3,Z=2,Dc=2.517g/cm3,F(000)=1970,μ(MoKα)=2.766mm-1,全矩阵最小二乘法修正至R=0.0832,wR=0.2638。标题化合物是由1个质子化的1,6-己二胺、12-钼磷混合价杂多阴离子[PMo12O40]4ˉ、3个水分子、2个乙醛分子和1个二甲基甲酰胺分子构成。     

Hydrothermal Synthesis, Crystal Structure and Magnetic Property of a Novel Mixed Valence Decatungstate:[Cu(2,2'-blpy)2]2Na2W6ⅤW4ⅥO30·2H2O

A metal-organic coordination polymer [Zn2.5(phen)(BDC)2(OH)]2 (phen = 1,10-phenanthroline, BDC = benzene-1,4-dicarboxylic acid)1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectro-scopy. The complex crystallizes in the triclinic system, space group P1 with a = 11.199(2), b =11.593(2), c = 11.865(3) A, α= 99.330(1), β=111.506(1),γ = 104.804(1)°, V= 1328.4(5) A3, Dc=1.722 g/cm3, Z = 1, Mr = 1377.82, F(000) = 692, μ(MoKa) = 2.306 mm-1, S = 1.093, R = 0.0281 and wR= 0.0756 for 4179 observed reflections (Ⅰ 20(Ⅰ)). The coordination polyhedron around Zn(Ⅱ)can be described as a tetrahedron, trigonal bipyramid and octahedron. It is worth noting that the crystal structure of 1 is composed of tetranuclear zinc clusters linked by {ZnO6} units.     

Hydrothermal Synthesis,Crystal Structure and Magnetic Property of a Novel Mixed Valence Decatungstate： [Cu（2,2＇-bipy）2]2Na2W6^VW4·VIO30·2H2O

A novel Cu（II）-2,2＇-bipy-supported （bipy = bipyridine） mixed valence decatungstate, [Cu（2,2＇-bipy）2]2Na2W6^VW4^VIO30·2H2O 1, has been synthesized and structurally characterized by X-ray analysis. The crystal of 1 is of triclinic, space group P1^- with a= 10.9393（10）, b = 12.0492（2）, c = 12.3783（2）A, a = 80.631（10）, β= 70.226（10）, γ= 72.329（9）^o, V = 1459.64（4）A^3, Z = 1, Dc = 3.582 g/cm^3, F（000） = 1404, R = 0.0553 and wR = 0.1242 for 4607 observed reflections （I 〉 2σ（I））. The EPR spectrum of 1 indicates that its unpaired electrons are placed in the dx2-y2 orbital of the ground state of Cun. Furthermore, compound 1 shows an antiferromagnetic interaction.     

基于水杨醛类席夫碱构筑的Fe(Ⅲ)、Co(Ⅲ)、混价Mn(Ⅱ))/Mn(Ⅲ)配合物的合成、晶体结构及磁性

以3-甲氧基水杨醛与乙醇胺缩合得到席夫碱化合物hmmpH_2(hmmpH_2=2-[(2-羟乙基亚氨基)甲基]-6-甲氧基苯酚),以hmmpH_2为配体合成了配合物[Fe_2(hmmp)_2(hmmpH)_2]·1.5CH_3CN·0.5H_2O(1)和[Co_2Na(hmmp)_2(N_3)_2(CH_3O)(CH_3OH)_2](2)。以3,5-二溴水杨醛与乙醇胺缩合得到化合物hmdbrpH_2(hmdbrpH_2=2-[(2-羟乙基亚氨基)甲基]-4,6-二溴苯酚),以hmdbrpH_2为配体合成了一个混价三核配合物[Mn(Ⅱ)Mn(Ⅲ)_2(hmdbrp)_2(O_2CPh)_4(CH_3OH)_2]·2CH_3CN·2CH_3OH(3)(HO_2CPh为苯甲酸)。对配合物分别进行了元素分析、X射线单晶衍射分析,还对1和3进行了磁性研究。单晶结构分析表明配合物1中2个六配位的Fe(Ⅲ)离子通过2个醇羟基氧原子相连形成二聚体结构,配合物2中Co(Ⅲ)也为六配位,通过2个甲醇中氧原子相连形成双核结构,配合物3为一混价三核锰结构,3个Mn离子呈线性排列。磁性测试表明配合物1中Fe(Ⅲ)离子之间存在反铁磁相互作用,配合物3的三核锰单元内Mn(Ⅱ)、Mn(Ⅲ)离子之间存在反铁磁相互作用。     

基于水杨醛类席夫碱构筑的Fe(Ⅲ)、Co(Ⅲ)、混价Mn(Ⅱ))/Mn(Ⅲ)配合物的合成、晶体结构及磁性

以3-甲氧基水杨醛与乙醇胺缩合得到席夫碱化合物hmmpH₂（hmmpH₂=2-[（2-羟乙基亚氨基）甲基]-6-甲氧基苯酚）,以hmmpH₂为配体合成了配合物[Fe₂（hmmp）₂（hmmpH）₂]·1.5CH₃CN·0.5H₂O（1）和[Co₂Na（hmmp）₂（N₃）₂（CH₃O）（CH₃OH）₂]（2）。以3,5-二溴水杨醛与乙醇胺缩合得到化合物hmdbrpH₂（hmdbrpH₂=2-[（2-羟乙基亚氨基）甲基]-4,6-二溴苯酚）,以hmdbrpH₂为配体合成了一个混价三核配合物[Mn（Ⅱ）Mn（Ⅲ）₂（hmdbrp）₂（O₂CPh）₄（CH₃OH）₂]·2CH₃CN·2CH₃OH（3）（HO₂CPh为苯甲酸）。对配合物分别进行了元素分析、X射线单晶衍射分析,还对1和3进行了磁性研究。单晶结构分析表明配合物1中2个六配位的Fe（Ⅲ）离子通过2个醇羟基氧原子相连形成二聚体结构,配合物2中Co（Ⅲ）也为六配位,通过2个甲醇中氧原子相连形成双核结构,配合物3为一混价三核锰结构,3个Mn离子呈线性排列。磁性测试表明配合物1中Fe（Ⅲ）离子之间存在反铁磁相互作用,配合物3的三核锰单元内Mn（Ⅱ）、Mn（Ⅲ）离子之间存在反铁磁相互作用。     

Organically Templated Vanadium Oxide Phases: Synthesis and Structures of [H3NCH2CH2NH3][V2O6] and [HN(CH2CH2)3NH][VV2VIV4O14]·H2O

The synthesis and crystal structures of [H₃NCH₂CH₂NH₃][V₂O₆] (1) and [HN(CH₂CH₂)₃NH][V^V ₂V^IV ₄O₁₄]·H₂O (2) are described. The structure of the oxidized compound 1 consists of parallel stacks of vanadium oxide chains of corner sharing {VO₄} tetrahedra. The chains are stabilized by extensive hydrogen bonding involving oxide ligands of the chains and ethylenediammonium ions which fill the space between the stacks of chains. The structure of compound 2 consists of vanadium oxide layers separated by doubly protonated 1,4-diazabicyclo[2.2.2]octane and lattice water. The vanadium oxide layers, containing mixed-valence vanadium (V^V and V^IV) centers, are composed of zigzag ribbons of edge-sharing {VO₅} square pyramids interconnected by {VO₄} tetrahedra. Crystal data. C₂H₁₀N₂O₆V₂ , 1: monoclinic, space group P2₁/c (No. 14), a=5.5359(5), b=12.9430(12), c=5.6856(5) Å, =90, =97.460(2), =90°, V=403.93(6) ų, Z=2. A total of 2506 reflections ( _max=27.89°) was collected, of which 954 were used to resolve the structure. The structure was solved by direct methods and least-squares refinement converged at R=0.0592. C₆H₁₆N₂O₁₅V₆, 2: monoclinic, space group C2 (No. 5), a=19.303(4), b=6.667(2), c=7.579(2) Å, =90, =111.31(2), =90°, V=908.4(4) ų, Z=2. A total of 1779 reflections was collected, of which 1591 unique reflections were used for structural elucidation. The structure was solved by direct methods and least-squares refinement converged at R=0.0314.     

一些大取代二茂铁三碘化物的合成和结构分析

合成了一系列大取代二茂铁三碘化物,通式为(RC~5H~4)~2FeI~3。通过元素分析,红外光谱,质谱,顺磁共振谱,穆斯堡尔谱和电导率对这些化合物进行了表征。测定了化合物[CH~2(CH~2)~3C(2-CH~2C~5H~4N)C~5H~4]~2FeI~4.H~2O的晶体结构,该晶体属三斜晶系,P-1空间群,晶胞参数:a=0.9593(1),b=1.3999(2),c=1.4537(2)nm。α=109.64(1),β=97.25(1),γ=104.69(1)ⅲ。V=1.7299nm^3,Mr=1030.13,Dx=1.98g/cm^3,Z=2。结果表明,取代二茂铁被碘部分氧化,导致中心金属铁表现为混合价态;由于茂环上大取代基的影响,使得I~3^-与I~3^-之间未能形成碘链,因此这些化合物的电导率很低。