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 Cu I ( b3pmdc ) architectures were isolated, as well as a single oxidized Cu II ( b3pmdc ) species. These include the helical one-dimensional (1D) chain [H 4 b3pmdc ][Cu 10 I 14 ]·CHCl 3 ·2H 2 O ( 1 ), the luminescent linear cluster chain [Cu 4 I 6 (H 2 b3pmdc )] ( 2 ), the guest water containing network [Cu 4 I 4 (H b3pmdc ) 2 ](1.5ClO 4 )(0.5I 3 )·3.5H 2 O·2.5MeOH ( 3 ), the luminescent cubane cluster chain [Cu 4 I 4 ( b3pmdc ) 2 ] ( 4 ), the three-dimensional (3D) net [Cu 9 I 12 (K b3pmdc ) 3 (H 2 O) 4 ]·9MeOH ( 5 ), the dinuclear mixed halide [Cu 2 Cl 3.4 I 2.6 (H 4 b3pmdc )] ( 6 ), and the cupric 1D chain [CuCl 2 (H 2 b3pmdc )(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, HClO 4 ). In the case of 2 and 4, green and yellow luminescent emission was observed, as a result of the varied metal environment.