铜配位聚合物[Cu(C5H6S5)(SCN)]∞的合成和结构研究(英)

The Copper(Ⅰ) supramolecular complexes of 4,5-bis(methylthio)-1,3-dithiole-2-thione (C₅H₆S₅), [Cu(C₅H₆S₅)(SCN)]_∞ 1 and [Cu(C₅H₆S₅)I]_∞ 2, have been prepared and characterized. X-ray structure analysis for complex 1 reveals that the infinite chain structure with polymeric stairs of different lengths is formed through the coordination mode (μ₃) of the thiocyanate bridges. The shorter interchain S…S contacts give rise to a three-dimensional network structure. CCDC: 215668.     

多硫二硫烯铜配合物(n-Bu4N)[Cu(cddt)2]和(Ph4P)[Cu(cddt)2]的合成、表征及其结构

Two copper complexes with a new multi-sulfur 1,2-dithiolene ligand, C[Cu(cddt)₂] (C=tetrabutylammoni-um, n-Bu₄N⁺; tetraphenylphosphonium, Ph₄P⁺; cddt = 4a, 6, 7, 7a-5H-cyclopenta[b]-1,4-dithiin-2,3 dithi-olate) have been synthesized and characterized by electrochemical studies, IR, EA, etc. The structure of (Ph₄P)[Cu(cddt)₂] was determined by single crystal X-ray analysis. The complex was crystallized in the triclinic, space group P1 with the cell dimensions a=10.460(2)?, b=13.000(3)?,c=16.270(3)?, α=86.68(3)°,β= 71.92(3)°,γ=66.66(3)° and Z=2. R₁=0.0548, wR₂=0.1358 for 6786 independent reflections. The four S atoms surround the Cu atom [CuS₄] core is a square-planar environment.     

自旋交叉配合物[Fe(mtt)(phen)(NCS)2]·py的合成和磁性研究

设计制备了一个新的自旋交叉配合物[Fe(mtt)(phen)(NCS)2·]py。通过元素分析、红外光谱、质谱和紫外光谱等方法对该配合物进行结构表征。变温磁化率研究发现该配合物的自旋转换温度为Tc↑=197K,Tc↓=188K,回滞宽度9K。通过与同体系其他配合物的比较发现,配体的修饰对自旋交叉临界温度以及回滞宽度都有显著影响。     

含樟脑衍生物氰基桥联双金属配合物的合成、结构及磁性质

采用樟脑衍生物为配体，分别合成了氰基桥联Cu(Ⅱ)-Fe(Ⅲ)-Cu(Ⅱ)三核配合物[{Cu(D,L-La)₂}₂Fe(CN)₆](ClO₄) (1)和Mn(Ⅲ)-Fe(Ⅲ)双核配合物[Mn(D,L-Lb)(DMF)(Tp)Fe(CN)₃]·(H₂O)₆ (2)。晶体结构分析表明，化合物1中Cu(Ⅱ)离子处于五配位的配位环境，分别和1个D-La，1个L-La及[Fe(CN)₆]^3-中的1个氰基配位，2个Cu(Ⅱ)离子通过[Fe(CN)₆]^3-桥联。通过分子间氢键作用，化合物1形成二维超分子网络结构。化合物2中，[(Tp)Fe(CN)₃]^-通过其中的1个氰基与[Mn(D，L-Lb)]⁺桥联，其中Mn(Ⅲ)离子为六配位，分别和四齿配体Lb的2个氧原子和2个氮原子、DMF的1个氧原子及[(Tp)Fe(CN)₃]^-中的氰基氮原子配位。磁性研究表明，在化合物1中，Cu(Ⅱ)离子与Fe(Ⅲ)离子之间表现出铁磁相互作用，用哈密顿函数H=-2J(S₁·S₂+S₂·S₃)对其χ_MT-T曲线进行拟合，得到1的朗日因子g为2.190，交换常数J为0.55 cm^-1。     

基于[(Tp)Fe(CN)3]-氰基桥联双核配合物的合成、结构和磁性研究

采用[TpFe^Ⅲ(CN)₃]^-作为构筑基块，合成并表征了一个氰基桥联双核配合物[(Tp)Fe^Ⅲ(CN)₃Cu^Ⅱ(bpy)₂]ClO₄·CH₃OH (1)。对化合物1进行了晶体结构分析，其晶胞参数为a=0.904 26(5) nm，b=1.352 56(7) nm，c=1.556 02(8) nm，α=106.08(1)°，β=95.79(1)°，γ=91.01(1)°，P1空间群。在这个化合物中，[TpFe^Ⅲ(CN)₃]通过其中1个氰基与[Cu(bpy)₂]²⁺桥联，而另外2个氰基未参与配位。磁性研究表明，在化合物1中，Cu(Ⅱ)与Fe(Ⅲ)离子之间表现为铁磁相互作用。用哈密顿函数H=-2JS_FeS_Cu对其χ_MT-T曲线进行了拟合，得到1的朗德因子g=2.34和交换常数J=5.52 cm^-1。     

A Mn(Ⅱ) Coordination Polymer with the Flexible Tripodal Ligand 1,3,5-Tris-(imidazol-1-ylmethyl)benzene

A new Mn(Ⅱ) coordination polymer {[Mn(timb)2(H2O)2]·(Cl)2·(H2O)2}n(1,timb = 1,3,5-tris-(imidazol-1-ylmethyl)benzene) has been synthesized and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1 with a=9.0774(13),b=9.8720(15),c=11.4898(16),α=93.378(3),β= 95.471(3),γ=101.101(3)°,V=1002.6(3)3,Mr=834.67,Dc=1.382 g/cm3,μ(MoKα)=0.517mm-1,F(000)=435,GOF=0.986,Z=1,the final R=0.0506 and wR=0.1139 for 3517 observed reflections I2σ(I).It consists of one-dimensional double stranded chains formed through bridging bidentate timb ligands,and these chains are further connected to yield a 3D supramolecular framework by hydrogen bonding interactions and π…π stacking interactions.     

一个新的双核双(μ-氧桥)锰(Ⅲ/Ⅳ)配合物的合成、结构和性质(英文)

二价锰盐和1,4,8,11-环十四四氮烷(cyclam)在溶液中自组装生成双核双(μ-氧桥)锰(Ⅲ/Ⅳ)配合物:犤(cyclam)MnO犦2(ClO4)2(NO3)。该配合物被晶体结构表征,低温EPR表明其具有16条Mn?/Mn?二聚体的特征信号。磁性研究确认有强的反铁磁性,J/k=-680K,g=2.0。