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Photochemically and Thermally Generated BN-Doped Borafluorenate Heterocycles via Intramolecular Staudinger-Type
Bi Youan E Tra1, Andrew Molino2, Kimberly K Hollister1
1Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Building 18-596, Cambridge, Massachusetts 02139-4307, United States.
Abstract:
A series of BN-incorporated borafluorenate heterocycles, bis(borafluorene-phosphinimine)s (11-15), have been formed via intramolecular Staudinger-type reactions. The reactions were promoted by light or heat using monodentate phosphine-stabilized 9-azido-9-borafluorenes (R3P-BF-N3; 6-10) and involve the release of dinitrogen (N2), migration of phosphine from boron to nitrogen, and oxidation of the phosphorus center (PIII to PV). Density functional theory (DFT) calculations provide mechanistic insight into the formation of these compounds. Compounds 11-15 are blue emissive in the solution and solid states with absolute quantum yields (ΦF) ranging from 12 to 68%.
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