Meso Alkynylated Tetraphenylethylene (TPE) and 2,3,3-Triphenylacrylonitrile (TPAN) Substituted BODIPYs

Abstract

The tetraphenylethylene (TPE) substituted BODIPY 2a, and 2,3,3-triphenylacrylonitrile (TPAN) substituted BODIPYs 2b and 2c were designed and synthesized by the Pd-catalyzed Sonogashira cross-coupling reaction. Their photophysical and electrochemical properties were investigated. The BODIPY 2a exhibits strong D-A interaction with poor fluorescence quantum yield. The BODIPYs 2b and 2c show red-shifted absorption and emission with higher fluorescence quantum yield compared to BODIPY 2a. The photonic properties of BODIPYs 2a-2c were compared with 4-ethynylbenzonitrile substituted BODIPY 3 and phenylacetylene substituted BODIPY 4. The results reveal that the electron donating group at the meso position of BODIPY blue shifts the absorption and emission with decreased fluorescence quantum yield, whereas the electron withdrawing group at the meso position of BODIPY red shifts the absorption and emission with enhanced quantum yields. The single crystal structures of BODIPYs 2a and 2b reflect the planar orientation of meso substituent and the BODIPY core, which leads to close π-π stacking. The extensive π-π stacking and strong donor-acceptor (D-A) interaction makes these BODIPYs AIE inactive. The experimental observations were supported by DFT calculation. © 2015 American Chemical Society.