Gao Xu-Sheng, Dai Hai-Jie, Ding Mei-Juan, Pei Wen-Bo, Ren Xiao-Ming
State Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry & Molecular Engineering , Nanjing Tech University , Nanjing 211816 , PR China.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering , Nanjing University , Nanjing 210023 , PR China.
Inorg Chem. 2019 May 20;58(10):6772-6780. doi: 10.1021/acs.inorgchem.9b00215. Epub 2019 May 9.
Two new Pb-based coordination polymers (CPs), [Pb(HBTC)(DMF)] (1) and [Pb(HPTC)] (2), have been synthesized under solvothermal condition; herein, HBTC and HPTC represent 1,3,5-benzenetricarboxylic acid and 2,4,6-pyridine tricarboxylic acid, respectively. Both 1 and 2 were characterized by microanalysis, infrared spectra (IR), thermal gravimetric analyses (TGA), and powder X-ray diffraction (PXRD) techniques. Single-crystal structural analysis indicates that 1 and 2 show different coordination sphere around Pb ions and distinct coordination frameworks. The IO type three-dimensional (3D) nonporous metal-organic framework forms in 1, where the Pb ion shows holo-directed coordination geometry, while the IO type two-dimensional (2D) coordination polymeric layered structure forms in 2, where Pb ion shows a hemidirected coordination sphere and the 6s lone electron pair in Pb ion is stereochemically active. The two CPs emit intense and long-lasting greenish phosphorescence in air at room temperature, with absolute quantum yields of 1.2% for 1 and 4.7% for 2 and decay lifetimes of 0.73 ms for 1 and 1.52 ms for 2.
在溶剂热条件下合成了两种新型的铅基配位聚合物（CPs），即[Pb(HBTC)(DMF)]（1）和[Pb(HPTC)]（2）；在此，HBTC和HPTC分别代表1,3,5-苯三甲酸和2,4,6-吡啶三甲酸。通过微量分析、红外光谱（IR）、热重分析（TGA）和粉末X射线衍射（PXRD）技术对1和2进行了表征。单晶结构分析表明，1和2在铅离子周围呈现出不同的配位环境和独特的配位框架。1中形成了IO型三维（3D）无孔金属有机骨架，其中铅离子呈现全向配位几何构型，而2中形成了IO型二维（2D）配位聚合物层状结构，其中铅离子呈现半向配位环境且铅离子中的6s孤对电子具有立体化学活性。这两种配位聚合物在室温下的空气中均发出强烈且持久的绿色磷光，1的绝对量子产率为1.2%；2的为4.7%，1的衰减寿命为0.73 ms，2的为1.52 ms。
