Assembly of Two Porous Cadmium(II) Frameworks: Selective Adsorption and Luminescent Property

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• 作者：Lili Wen ; Xiaohuan Ke ; Ling Qiu ; Yang Zou ; Li Zhou ; Jinbo Zhao ; Dongfeng Li
• 刊名：Crystal Growth & Design
• 出版年：2012
• 出版时间：August 1, 2012
• 年：2012
• 卷：12
• 期：8
• 页码：4083-4089
• 全文大小：446K
• 年卷期：v.12,no.8(August 1, 2012)
• ISSN：1528-7505

文摘

Two microporous cadmium(II) metal鈥搊rganic frameworks, [Cd(cptpy)(Ac)(H₂O)路(DMA)(H₂O)]_n (1) and [Cd(cptpy)₂路(DMF)₂]_n (2) (Hcptpy = 4-(4-carboxyphenyl)-2,2鈥?4鈥?4鈥?terpyridine, DMA = N,N-dimethylacetamide, DMF = dimethylformamide) have been solvothermally synthesized under different reaction conditions. Complex 1 is a double-interpenetrating 3D network, while 2 is a noninterpenetrating (3,5)-connected 2D framework. The dehydrated forms of compounds 1 and 2 exhibit selective adsorption of CO₂ over N₂ and H₂O over CH₃OH. In addition, the adsorption value of CO₂ for 2 is higher than that of 1. The contents of uncoordinated pyridine nitrogen (Lewis basic sites) per formula unit of 1 and 2 are 2.16 and 4.36%, respectively. Obviously, the grafting of more uncoordinated pyridine nitrogen into compound 2 could enhance adsorption of the acidic CO₂ molecule. Notably, both 1 and 2 display strong photoluminescence. The nature of electronic transitions for complex 1 in the photoluminescent process was investigated by means of time-dependent density functional theory (TDDFT) calculations and molecular orbital analyses, which collaborates that the luminescent property is ligand-based.