ZnS:Cr2+晶体中Cr2+杂质离子的EPR参量及其占位

本文基于 ZnS:Cr²⁺晶体中 Cr²⁺杂质离子处于八面体有效晶场(D_2d畸变)理论模型,通过考虑对基态有较大影响的所有低自旋态的贡献后,建立了一组维数较大曲 d⁴(D_2d^*)不可约表示强场能量矩阵.利用矩阵的特征值、特征矢量以及相应的EPR 参量理论公式,对 ZnS:Cr²⁺晶体的精细光谱、基态 ZFS,EPR 参量(g,g,D,E,F,α)、基态 Zeeman 能级以及 EPR 条件(B,v)进行了系统的理论分析与计算.结果与实验值符合很好.从而确立了 ZnS:Cr²⁺晶体中 Cr²⁺杂质离子的环境晶场系 D_2d畸变八面体结构.ZnS:Cr²⁺晶体的光、磁性质与 Cr²⁺杂质离子的八面体晶场结构特征密切相关.     

3-甲基-4-对甲基苯基-5-(2-吡啶基)-1，2，4-三唑双核锰(Ⅱ)配合物的合成及晶体结构

A dinuclear Mn(Ⅱ) complex [Mn₂L₂(μ-Cl)₂Cl₂(H₂O)₂] (1) was synthesized by reaction of ligand L with MnCl₂ ·4H₂O and its structure was determined by X-ray crystal structure analysis. The structure indicates that the complex crystallizes in monoclinic, space group C2/c with a=2.018 0(15) nm, b=0.894 0(6) nm, c=1.932 1(14) nm, β=97.506(12)°. V=3 456(4) nm3, Z=4, D_c=1.515 Mg·m^-3, μ=1.081 mm^-1, F(000)=1 608, and final R₁=0.043 8, wR₂=0.109 9. The result shows a Mn(Ⅱ) ion was six-coordinated by a bidentate 3-methyl-4-( p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole, one chlorine and one bridging chlorine atom in the basal positions and one chloride atom and one water molecule in the axial one, to form a distorted octahedral-pyramidal geometry. CCDC: 713047.     

3-甲基-4-对甲苯基-5-(2-吡啶基)-1，2，4-三唑-铜(Ⅱ)配合物

A copper(Ⅱ) complex [CuL(H₂O)(Sal)]·0.5H₂O was obtained by the reaction of copper(Ⅱ) salicylate with 3-methyl-4-(4-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole (L) in ethanol-water solution at room temperature. The crystal belongs to triclinic system with space group P1, and a=0.913 6(4) nm, b=1.122 2(5) nm, c=1.263 3(7) nm, α=67.10(2)°, β=76.31(3)°, γ=68.17(2)°, V= 1.101(1) nm³, Z=2. The final refinement gave R₁=0.039 8 and wR₂=0.106 0 for 3 453 reflections with I>2σ(I). This complex is a good purple fluorescent material in solid state at room temperat-ure. CCDC: 685713.     

d8(C3v*)EPR理论与CsMgCl3:Ni2+的光、磁性质研究

本文给出了O_h点群表象中的d^2,8(C_3v^*)完全强场矩阵,并借助于这种矩阵的特征值和特征矢量,建立了CsMgX₃:Ni²⁺(X=Cl,B,I)类晶体的全组态混合EPR理论。应用这一理论,对CsMgCl₃晶体中的Ni²⁺杂质离子的光学吸收谱、基态零场分裂参量D、顺磁g因数、基态Zeeman分裂以及EPR条件(B,hv₀)进行了统一的计算。结果与观测非常一致,从而首次对CsMgCl₃:Ni²⁺的光、磁性质作出了统一的理论解释。     

3-甲基-4-对甲基苯基-5-(2-吡啶基)-1，2，4-三唑双核铜(Ⅱ)配合物的合成、晶体结构及磁性

A dinuclear Cu(Ⅱ) complex [Cu₂(MMBPT)₂Cl₄(H₂O)_2.5] (I) [MMBPT=3-Methyl-4-(4-Methylphenyl)-5-(2-pyridyl)-1,2,4-triazole] was synthesized by reaction of MMBPT with CuCl₂·2H₂O and its structure was determined by X-ray crystal structure analysis. The structure indicates that the complex crystallizes in monoclinic, space group P2₁/c with a=1.273 4(3) nm, b=1.237 5(3) nm, c=2.403 2(5) nm, β=90.51(3)°. V=3.786 6(13) nm³, Z=2, D_c=1.429 Mg·m^-3, μ=1.445 mm^-1, F(000)=1 660, and final R₁=0.055 5, wR₂=0.129 7. The crystal structure shows that the dinuclear Cu₂N₆ unit is almost planar in which each Cu(Ⅱ) ion was five-coordinated by one nitrogen atoms from MMBPT and two chlorine in the basal positions and two nitrogen atoms from two MMBPTs respectively in the axial one, to form a distorted trigonal bipyramidal geometry. Magnetic measurements reveal a relatively strong antiferromagentic interaction in the complex. CCDC: 720011.