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.