基于d¹⁰金属卤化物和双（苯并三氮唑）烷烃配位聚合物的合成、结构及性能研究

【作者】 高霞；

【导师】 胡满成； 翟全国；

【作者基本信息】 陕西师范大学 ， 无机化学， 2010， 硕士

【摘要】 本文在溶剂热条件下,以自制的柔性1,2-双(苯并三氮唑)乙烷(L1),1,3-双(苯并三氮唑)丙烷(L2),1,4-双(苯并三氮唑)丁烷(L3)和1,6-双(苯并三氮唑)已烷(L4)为桥联配体,以卤素离子为第二桥联配体,分别与d10过渡金属Cu(I)和Cd(II)合成了10个结构新颖的掺杂化合物,分别为：{CdI2]2(L1)2}(1),{[CdBr2]3(L1)2}.(2),{[CdI2](L2)}n.(3),{[CdBr2](L3)}n.(4), {[CdBr2]2(L4)2}.(5),{[CdI2]4(L4)4}n.(6),{[CdCI2]5(L1)2).(7),{[CuCl]2(L4)}n.(8), {(HETA)[(Cu6I7)(ETA)2]}n.(9)和{K(Cu6Br7)(L4)}.(10),采用X-射线单晶衍射对它们的单晶结构进行了确定。化合物1-7为系列Cd(II)化合物,均属单斜晶系。化合物1,2和7均属C2／c空间群；化合物3和4均属P2(1)／c空间群；化合物5和6分别属P2(1)In和Cc空间群。除化合物1和7分别为零维和二维结构外,其余化合物均为一维结构。其中化合物1是[Cdl2(L1)]2双核单元零维结构；化合物2是由μ2桥联的L1配体连接一维[CdBr2]无机链形成的一维有机无机链状结构；化合物3和4均是由有机配体采取μ2桥联模式连接[CdX2]无机单元而形成的无限链状结构；化合物5中同时存在有[Cd-Br-Cd-Br]的无机菱形结构和[Cd-L4-Cd-L4]双核单元,二者交替连接构成一维无限链状结构；化合物6先是由独立的Cd1,Cd2,Cd3和Cd4连接L4配体形成平行四边形的[Cd4(L4)4]环状结构,然后相邻环状结构之间通过另一个独立配体L4连接而形成的一维无限带状结构；化合物7是由μ2桥联的L1配体连接由缺位立方烷单元[Cd3Cl4]构筑的一维无机带状结构而形成的二维网状结构。化合物8-10均是首次以1,6-双(苯并三氮唑)已烷(L4)为配体而形成的Cu(I)化合物。化合物8属四方晶系,I4(1)／a空间群；化合物9和10均属单斜晶系,分别为C2／c和P2(1)／m空间群。化合物8是以μ4桥联的L4配体连接一维[CuCl]n无机链形成三维结构；化合物9和10中首次出现了新颖的[Cu6IX7]nn-(X=C1,Br)阴离子链,其中化合物9由新颖的一维有机阴离子链[(Cu6I7)(ETA)2]nn-和质子化的有机阳离子HETA组成,而化合物10是由一维[Cu6Br7]nn-阴离子链通过与七配位的K原子相连接形成二维的[KCu6Br7]层状结构,然后L4配体采用μ4桥联与该层状结构相连接。本文对配体L1-L4及化合物1-10进行了元素分析、热重分析、红外光谱、X-射线粉末衍射、半导体和荧光性能等全面的理化性能研究,同时还针对化合物中存在的弱相互作用以及配体采取的构象进行了研究。更多还原

【Abstract】 In the work,the self-assemblies of 1,2-bis(benzotriazol)ethane(L1), 1,3-bis(benzotriazol)propane (L2), 1,4-bis(benzotriazol)butane (L3), 1,6-bis(benzotriazol)hexane (L4) flexible ligands with CuX or CdX2 (X=Cl-, Br- and I-) under solvo-thermal conditions produced 10 coordination polymers, namely,{[CdI2]2(L1)2} (1),{[CdBr2]3(L1)2}n (2), {[CdI2](L2)}n(3),{[CdBr2](L3)}n(4),{[CdBr2]2(L4)2}n(5),{[CdI2]4(L4)4}n(6),{[CdCl2]5(L1)2}n (7),{[CuCl]2(L4)}n(8),{(HETA)[(Cu6I7)(ETA)2]}n(9) and {K(Cu6Br7)(L4)}n(10). Their crystal structures have been determined by X-ray single-crystal diffraction.Complexes 1-7 are of Cd (Ⅱ) compounds, which crystallize in the monoclinic space group C2/c (1,2 and 7), P2(1)/c (3 and 4), P2(1)/n (5) and Cc (6), respectivelly. Complex 1 is of a 0-D binuclear structure; Complexes 2,3 and 4 all show 1-D chain structures; The rhomboid [Cd-Br-Cd-Br] binuclear unit and [Cd-L4-Cd-L4] binuclear subunit are linked alternately to form the 1-D chain structure for complex 5; Complex 6 is a 1-D ribbon structure with adjacent large ring subunits [Cd4(L4)4] connected by another independent L4 ligand; Complex 7 is a 2-D net structure constructed fromμ2-bridging L1 ligands and 1-D ribbon structures consists of vertex missing cubane-like [Cd3Cl4]subunits.Complexes 8-10 are of Cu (I) compounds, firstly generated using 1,6-bis(benzotriazol)hexane (L4) as the ligand. Complex 8 crystallizes in the tetragonal space group 14(1)/a, while complexes 9 and 10 crystallize in the monoclinic space group C2/c and P2(1)/m, respectively. Complex 8 builds up byμ4-bridging L4 ligands and 1-D [CuCl] inorganic chains and made a 3-D structure; Complexes 9 and 10 both are constucted from novel [Cu16X7]nn-(X=Cl,Br) inorganic anionic chain, compound 9 shows a supramolecular structure consisting of 1-D anionic organic-inorganic hybrid [(Cu6I7)(ETA)2]nn- chains and disordered protonated HETA organic cations, while compound 10 is constructed by (μ4-bridging L4 ligand and 2-D neutral inorganic [KCu6Br7] layer. Such layer consists 1-D anionic [Cu6Br7]nn-chains and heptacoordinated K atoms.Complexes 1-10 have been characterized by X-ray powder diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis, UV-vis diffuse reflectance spectrum and photoluminescence measurements. What’s more, weak interaction that exists in these complexes and the ligand conformation have also been studied.更多还原