摘要
以2-氨基-4-噻唑乙酸乙酯(EATA)和氯化镉水合物为原料,在无水乙醇和乙醇-水混合物两种溶剂中分别合成了配合物[CdCl2(EATA)]n(1)和[CdCl2(EATA)2](2),并利用X-射线单晶衍射、元素分析、红外光谱和荧光光谱对它们进行了表征。配合物1和2都属于单斜晶系,分别为P21/c和Cc空间群,它们的中心金属离子Cd2+均为扭曲的六配位八面体构型。在配合物1中,相邻的2个八面体单元通过2个μ2-Cl-阴离子双桥连形成一维链结构,该一维链进一步通过N-H…Cl分子间氢键形成了三维网络结构,而配合物2则通过大量的N-H…Cl和C-H…Cl分子间氢键等弱作用组装成二维超分子结构。固态荧光光谱分析表明,配合物1和2荧光性质相似,均可归属于由配体到金属间的电荷转移(LMCT)。
Two cadmium complexes, [CdCl2(EATA)]n(1) and [CdCl2(EATA)2](2), have been synthesized by the reaction between CdCl2·2.5H2O and ethyl 2-amino-4-thiazoleacetate (EATA), and characterized by single-crystal X-ray diffraction, elemental analysis, infrared and photoluminescence spectra. Single crystal X-ray diffraction analysis reveals that, complex 1 crystallizes in monoclinic with space group P21/c, a=1.765 1(5) nm, b=0.927 7(3) nm, c=0.715 0(2) nm, β=92.072(5)°, V=1.170 0(6) nm3, Z=4, R1=0.0363, wR2=0.0762, S=1.082. The title complex 2 also belongs to the monoclinic system, space group Cc with a=1.686 0(3) nm, b=1.663 0(3) nm, c=1.622 0(3) nm, β=105.41(3)°, V=4.384 3(15) nm3, Z=8, R1=0.0215, wR2=0.0483, S=1.021. For either complexes 1 or 2, the central metal ion (Cd2+) displays a distorted six-coordinated octahedral geometry. In complex 1, two adjacent octahedral units are connected by two bridging μ2-Cl- anions, resulting in the formation of one-dimensional chain. These one-dimensional chains are further assembled into a three-dimensional network structure by intermolecular N-H…Cl hydrogen bonds interactions. In complex 2, two-dimensional supramolecular structure is generated via a large number of intermolecular N-H…Cl and C-H…Cl hydrogen bonds. Solid-state photoluminescence spectrum shows that complexes 1 and 2 have similar fluorescence behaviors, and both of which can be attributed to the ligand-to-metal charge transition (LMCT). CCDC: 837325, 1; 837326, 2.
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
2014年第3期550-556,共7页
Chinese Journal of Inorganic Chemistry
基金
江西省教育厅科技项目(No.GJJ13711
GJJ10613)
江西省自然科学基金(No.20122BAB203002
20132BAB203003)
江西省科技厅科技计划指导性项目(No.2012zbbe50006)
上饶师范学院博士启动基金
材料物理与化学重点学科科研资助项目
关键词
镉配合物
合成
晶体结构
荧光
2-氨基-4-噻唑乙酸乙酯
cadmium complex synthesis crystal structure luminescent property ethyl 2-amino-4-thiazoleacetate