Developing synthetic host systems that are capable of binding to specifically targeted substrates and then mimicking the various chemical processes in nature have long been significant goals in chemistry. The construction of receptors that can encapsulate anionic species and sensitize their reaction is challenging and there is no report until now. We present the versatile preparation of a nanometer-sized macrocycle based on a photoactive porphyrin moiety and on cationic triazolium and pyridinium units by taking advantage of the Cu(I)-catalyzed �click chemistry�. The anion-binding properties of this cationic macrocyclic host are verified and then employed together with the photochemical porphyrin to establish the use of this molecular container as a reactor for the dimerization of 7,7,8,8-tetracyano-para-quinodimethane (TCNQ) radical anions. There is clear evidence for a rate increase of over two orders of magnitude, photosensitization of the host and demonstrated turnover of the catalyst. This approach is of great significance for the development of novel nanoscale devices capable of supramolecular catalysis. Li, Y. L.; Flood, A. H. Angew. Chem. Int. Ed., 2008 , 47, 2649.Zhao, Y. J.;  Li, Y. L.;  Li, Y. J.; Zheng, H.Y.; Yin, X. D.; Liu, H. B. Chem. Commun., 2010 , 46, 5698.Zhao, Y. J.;  Li, Y. L.; Li, Y. J.; Huang, C. S.;  Liu, H. B.; Lai, S. W.; Che, C. M.; Zhu, D. B.Org. Biomol. Chem., 2010 ,  8, 3923.Li, Y. J. ; Zhao, Y. J. ; Flood, A. H. ;Liu, C. ; Liu, H. B. ; Li, Y. L. Chem Eur J, 2011 , 17, 7499.

Nanometer-sized reactor: A porphyrin-based model system for anion species

245th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.