Porous organic frameworks (POFs) have attracted significant attention for the last decade due to their high surface area, permanent micro-/meso-pore structure, chemical and thermal stability, and highly tunable functionality of skeleton and pore environment. They have been widely studied for their potential applications in gas adsorption and storage, heterogeneous catalysis, chemical sensing, and energy related research.1 In particular, POFs with extended pi-conjugated fashion (also known as conjugated microporous polymers, CMPs) have intriguing physioptical properties that can be finely tuned by variety of organic building blocks and utilized as photocatalysts. However, the photocatalytic properties of pi-conjugated POFs are rarely studied despite of their additional advantages of low prices, high stability, and recyclability compared with commonly used transition-metal (e.g. Ru and Ir) complexes.2 In this presentation, a pyrene-based POF (Py-POF) as a metal-free heterogeneous visible-light photoredox catalyst will be presented. Photoredox catalysis is recently emerging as a powerful synthetic methodology for carbon-carbon bonds and carbon-heteroatom bonds formation.3 Imines, the important family of intermediates for nucleophilic addition and cycloaddition, have also successfully been synthesized by photoredox catalysis. Here, a detailed mechanistic study of using Py-POF catalyzes the imine formation from primary amine under air and room temperature will be discussed.4 [1] a) Xu, Y.; Jin, S.; Xu, H.; Nagai, A.; Jiang, D. Chem. Soc. Rev., 2013, 42, 8012; b) Wu, D.; Xu, F.; Sun, B.; Fu, R.; He, H.; Matyjaszewski, K. Chem. Rev., 2012, 112, 3959; c) Lu, J.; Zhang, J. J. Mater. Chem. A, 2014, 2, 13831; d) Zhang, X.; Lu, J.; Zhang, J. Chem. Mater., 2014, 26, 4023; e) Lin, Q.; Lu, J.; Yang, Z.; Zeng, X. C.; Zhang, J. J. Mater. Chem. A, 2014, 2, 14876. [2] Xie, Z.; Wang, C.; deKrafft, K. E.; Lin, W. J. Am. Chem. Soc., 2011, 133, 2056. [3] a) Schultz, D. M.; Yoon, T. P. Science, 2014, 343, 1239176; b) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. Chem Rev, 2013, 113, 5322. [4] Lu, J.; Zhang, J. Manuscript in prepraration.

Pyrene-based porous organic framework for efficient heterogeneous visible-light photocatalysis

249th National Meeting (2015)

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