Tripod molecules build molecular networks and open-dimer capsules by weak interactions  

作　　者：HAN Jun1, DENG Chao1, FANG Ru1, LI YiZhi2, WANG LeYong1& PAN Yi2 1Key Laboratory of Mesoscopic Chemistry, Ministry of Education School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China 2State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China 

出　　处：《Science China Chemistry》2010年第4期851-857,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (Grant Nos. 20602017 & 20932004);the National Basic Research Program of China (Grant No. 2007CB925103);the Natural Science Foundation of Jiangsu (Grant No. BK2008259)

摘　　要：Three tripod molecules, tris(2-methoxy-5-nitrobenzyl)phosphine oxide (1), tris(2-butoxy-3-methyl-5-nitrobenzyl)phosphine oxide (2), and tris(3-nitrobenzyl)amine (TNBA), were synthesized and crystallized. The structures of 1, 2, and their comparison (TNBA) were determined by X-ray crystallography. It is noteworthy that compound 1 interacted with adjacent molecules via π-π stacking and C-H···π interactions to yield an open supramolecular network with the porosity P in 8.9%, whereas compound 2 gathered closely to form an open-dimer capsule by sixfold N-O···π and triple C-H···O interactions, which showed a rare example of a stable in, out-invertomer of phosphine inversion existing in open-dimers. A series of columns were built and arranged side by side by these weak interactions. By contrast, TNBA crystallized to form a 2D network maintained by C-H···O and C-H···πinteractions. It seems minor changes of the chemical structure may cause large differences in the crystal structure and interactions in crystal engineering.Three tripod molecules, tris(2-methoxy-5-nitrobenzyl)phosphine oxide (1), tris(2-butoxy-3-methyl-5-nitrobenzyl)phosphine oxide (2), and tris(3-nitrobenzyl)amine (TNBA), were synthesized and crystallized. The structures of 1, 2, and their comparison (TNBA) were determined by X-ray crystallography. It is noteworthy that compound 1 interacted with adjacent molecules via π-π stacking and C-H···π interactions to yield an open supramolecular network with the porosity P in 8.9%, whereas compound 2 gathered closely to form an open-dimer capsule by sixfold N-O···π and triple C-H···O interactions, which showed a rare example of a stable in, out-invertomer of phosphine inversion existing in open-dimers. A series of columns were built and arranged side by side by these weak interactions. By contrast, TNBA crystallized to form a 2D network maintained by C-H···O and C-H···πinteractions. It seems minor changes of the chemical structure may cause large differences in the crystal structure and interactions in crystal engineering.

关 键 词：TRIPOD molecule SUPRAMOLECULAR network open-dimer capsule weak interaction 

分 类 号：O621.2[理学—有机化学]