New Molecular Rectangles and Coordination Polymers Constructed from Binuclear Phenoxo-Bridged [Cu2] and [Zn2] Tectons

The self-assembly processes between binuclear [Zn2] and [Cu2] complex cations and exo-bidentate ligands [trans-4,4′-azo-pyridine (azpy), 4,4′-bipyridine (4,4′-bipy), 1,2-bis(4-pyridyl)ethane (bpeta), 1,3-bis(4-pyridyl)propane (bpp)] generate two types of complexes: tetranuclear species with a rectangular topology and one-dimensional (1-D) coordination polymers: [{L2(μ-OH)Cu2}(μ-azpy)2{Cu2(μ-OH)L2}][{L2(μ-OH)Cu2(H2O)}(μ-azpy)2{(H2O)Cu2(μ-OH)L2}](ClO4)8 (1); [{L1Cu2(H2O)2}(μ-azpy)2{Cu2L1(H2O)2}](ClO4)4·(azpy)·2H2O (2); 1 ∞[{Cu2(μ-OH)L3}(μ-bpp)](ClO4)2 (3); 1 ∞[{L3Zn2(μ-OH)}(μ-4,4′-bipy)](ClO4)2·2H2O (4); 1 ∞[{L3Zn2(μ-OH)}(μ-bpeta)](ClO4)2 (5a); 1 ∞[{L3Zn2(μ-OH)}(μ-bpeta)](ClO4)2·THF (5b); 1 ∞[{L2Zn2(μ-OH)}(μ-4,4′-bipy)2](ClO4)2·2H2O (6) (H2L n are compartmental Schiff-base ligands resulting from condensation reactions between 2,6-diformyl-p-cresol with, respectively, 1,3-diamino-propane, 2-aminoethyl-pyridine, and N,N-dimethyl-ethylenediamine). The zinc complexes exhibit luminescence properties.