Synthesis and Optical Properties of Mono- and Diaminocorannulenes

The synthesis and luminescence properties of a series of mono- and diaminocorannulenes are described herein. Their synthesis from halocorannulenes is straightforward. Evaluation of their luminescence leads to three surprising discoveries. First, a wide range of mono- and diaminocorannulenes are far more fluorescent in solution than corannulene itself, and 4a-j and 5a-d are also fluorescent in the solid state. Second, we have identified a diaminocorannulene possessing what we now regard as“typical”green-yellow fluorescence in solution (λem = 552 nm), but exhibits orange-red fluorescence in the solid state (λem = 615 nm). Third, we have discovered ethylenediamine corannulene derivatives that are simultaneously water soluble and brightly fluorescent (λem = 517 nm, QY = 9%； λem = 560 nm, QY = 11%). These surprising discoveries have implications for corannulene-based materials and biological applications.