Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels

The variable-length azacrown ether bridging ligand N,N′-bis­(3-pyridyl-methyl)­diaza-18-crown-6
(b3pmdc) was reacted with cuprous iodide to give a range
of new discrete and polymeric coordination compounds. Six structurally
diverse CuI(b3pmdc) architectures were isolated,
as well as a single oxidized CuII(b3pmdc)
species. These include the helical one-dimensional (1D) chain [H4b3pmdc]­[Cu10I14]·CHCl3·2H2O (1), the luminescent linear
cluster chain [Cu4I6(H2b3pmdc)] (2), the guest water containing network [Cu4I4(Hb3pmdc)2]­(1.5ClO4)­(0.5I3)·3.5H2O·2.5MeOH
(3), the luminescent cubane cluster chain [Cu4I4(b3pmdc)2] (4),
the three-dimensional (3D) net [Cu9I12(Kb3pmdc)3(H2O)4]·9MeOH
(5), the dinuclear mixed halide [Cu2Cl3.4I2.6(H4b3pmdc)] (6), and the cupric 1D chain [CuCl2(H2b3pmdc)­(MeOH)2]·2Cl·2MeCN
(7). Manipulation of the ligand conformation was achieved
by the addition of the alkali metal salt potassium and by varying
the pH of the solution with a range of acids (HCl, HClO4). In the case of 2 and 4, green and yellow
luminescent emission was observed, as a result of the varied metal
environment.

将可变长度氮杂冠醚桥联配体N,N'-双(3-吡啶基甲基)二氮杂-18-冠-6（b3pmdc）与碘化亚铜反应，得到一系列新型离散型与聚合型配位化合物。成功分离得到六种结构各异的CuI(b3pmdc)配位骨架，以及一种氧化态的CuII(b3pmdc)物种，其中包括螺旋状一维（1D）链状配合物[H4b3pmdc][Cu10I14]·CHCl3·2H2O（1）、发光线性簇链配合物[Cu4I6(H2b3pmdc)]（2）、含客体水的配位网络[Cu4I4(Hb3pmdc)2]·(1.5ClO4)·(0.5I3)·3.5H2O·2.5MeOH（3）、发光立方烷簇链配合物[Cu4I4(b3pmdc)2]（4）、三维（3D）网状配合物[Cu9I12(Kb3pmdc)3(H2O)4]·9MeOH（5）、双核混合卤化物配合物[Cu2Cl3.4I2.6(H4b3pmdc)]（6），以及铜(II)基一维链状配合物[CuCl2(H2b3pmdc)(MeOH)2]·2Cl·2MeCN（7）。通过添加碱金属钾盐，并使用多种酸（HCl、HClO4）调节溶液pH，可实现配体构象的精准调控。针对化合物2与4，观测到因金属配位环境差异而产生的绿色与黄色发光发射现象。