Syntheses, Structures, and Photoluminescence of Three Coordination Polymers of Cadmium Dicarboxylates

Solvothermal reactions of 2,2‘-dihydroxy-[1,1‘]-binaphthalene-3,3‘-dicarboxylate (H4bna), 4,4‘-bipyridine (bpy), and
Cd2+ salts at different conditions yielded three new one- to three-dimensional coordination polymers, ∞[Cd(H2bna)(bpy)1.5(H2O)2]
(1), ∞3[Cd6(MeCO2)4(bpy)2(H2bna)4]·3.5H2O (2), and ∞[Cd6(bna)(H2bna)(bpy)(C2H5OH)] (3). Crystal structural analyses revealed
that 1 is an unusual bpy-bridged ladder structure with carboxylate-end coordinated H2bna ligands as lateral arms, 2 is a three-dimensional α-Po network structure comprised of new hexanuclear [Cd6(μ-MeCO2)2(μ3-MeCO2)2]8+ clusters as the nodes and multiple
H2bna and bpy as the linkers, whereas 3 exhibits a layer structure featuring bna-, H2bna-, and bpy-bridged infinite Cd−O ribbons.
These compounds also displayed structure-related photoluminescence properties in the solid state.

在不同溶剂热条件下，以2,2'-二羟基-[1,1'-联萘]-3,3'-二羧酸（H4bna）、4,4'-联吡啶（bpy）与二价镉盐为原料反应，得到三种新型1至3维配位聚合物：∞[Cd(H₂bna)(bpy)₁.₅(H₂O)₂]（1）、∞³[Cd₆(MeCO₂)₄(bpy)₂(H₂bna)₄]·3.5H₂O（2）以及∞[Cd₆(bna)(H₂bna)(bpy)(C₂H₅OH)]（3）。晶体结构解析表明，化合物1为一种罕见的bpy桥联梯状结构，其中以羧基端配位的H₂bna配体作为侧臂；化合物2为以新型六核[Cd₆(μ-MeCO₂)₂(μ₃-MeCO₂)₂]⁸⁺簇作为结构节点，辅以多组H₂bna与bpy作为桥联配体构建的三维α-钋（α-Po）拓扑网络结构；而化合物3则呈现出由bna⁻、H₂bna与bpy共同桥联的无限Cd-O链带构成的层状结构。上述三种化合物在固态下均表现出与自身结构相关的光致发光特性。