Polymeric Zn(II) and Cd(II) Sulfates with Bipyridine and Dioxime Ligands: Supramolecular Isomerism, Chirality, and Luminescence

The interaction of zinc(II) or cadmium(II) sulfate with 4,4′-bipyridine (bpy) or 4,4′-bipyridinethane (bpe) in the presence of 1,2-cyclohexanedionedioxime (NioxH2) resulted in four novel polymeric compounds with the compositions {[Zn(H2O)6][Zn(SO4)2(H2O)2(bpy)][Zn(SO4)(H2O)3(bpy)]}∞ (1), {[Zn(SO4)(NioxH2)(bpy)]·0.5H2O·DMF}∞ (DMF = N,N-dimethylformamide) (2), [Zn(SO4)(NioxH2)(bpe)]∞ (3), and [Cd(SO4)(NioxH2)(bpe)]∞ (4). Compounds were characterized by spectroscopic techniques and single crystal X-ray method. The chiral layer coordination polymer is the robust structural motif in 2–4. Although compounds 3 and 4 were isolated in the same crystallization conditions, the layers of opposite chirality constitute the achiral (3), and the layers of the same chirality result in chiral (4) architectures. All materials display blue luminescence upon excitation with ultraviolet light.

将硫酸锌(II)或硫酸镉(II)与4,4'-联吡啶（4,4′-bipyridine，简称bpy）或4,4'-联吡啶乙烷（4,4′-bipyridinethane，简称bpe）在1,2-环己二酮二肟（1,2-cyclohexanedionedioxime，简称NioxH2）存在下反应，得到四种新型配位聚合物，其组成分别为{[Zn(H₂O)₆][Zn(SO₄)₂(H₂O)₂(bpy)][Zn(SO₄)(H₂O)₃(bpy)]}∞（1）、{[Zn(SO₄)(NioxH₂)(bpy)]·0.5H₂O·DMF}∞（其中DMF为N,N-二甲基甲酰胺，2）、[Zn(SO₄)(NioxH₂)(bpe)]∞（3）以及[Cd(SO₄)(NioxH₂)(bpe)]∞（4）。所有化合物均通过光谱技术与单晶X射线衍射法进行表征。化合物2至4的稳定结构基元为手性层状配位聚合物。尽管化合物3与4在相同结晶条件下分离得到，但由相反手性层构成的化合物3为非手性结构，而由相同手性层构成的化合物4则为手性结构。所有材料在紫外光激发下均展现出蓝色发光性能。