Regioselectively Halogenated Expanded Porphyrinoids as Building Blocks for Constructing Porphyrin–Porphyrinoid Heterodyads with Tunable Energy Transfer

• DOI: 10.1021/jacs.8b13148
• Publication Date: 2019-03-09T01:49:26Z
• Authors: Qizhao Li; Chengjie Li; Jinseok Kim; Masatoshi Ishida; Xin Li; Tingting Gu; Xu Liang; Weihua Zhu; Hans Ågren; Dongho Kim; Hiroyuki Furuta; Yongshu Xie
• Keywords: Sonogashira coupling; Surface Modification

Expanded porphyrins have been attracting increasing attention owing to their unique optical and electrochemical properties as well switchable aromaticity. Toward material applications, regioselective functionalization of the expanded at periphery is indeed challenging due presence multiple reactive sites. Herein, a set halogenated isomers (L5-Br-A/B/C) neo-confused isosmaragdyrin (L5) are synthesized by combination halogenation reaction L5 sequential macrocycle-to-macrocycle transformation reactions its isomers. On this basis, regioselectively functionalized isosmaragdyrins utilized building blocks for constructing multichromophoric porphyrinoids, specifically, heterodyads L5-ZnP-A/B/C, in which common zinc porphyrin linked three different pyrrolic positions isosmaragdyrins, respectively, Sonogashira coupling reactions. The highly efficient energy cascade from elucidated using steady-state/time-resolved spectroscopies theoretical calculations. Notably, transfer processes moieties excitation rates L5-ZnP-A/B/C dependent on linking sites through-bond Förster-type resonance mechanisms. site-selective subsequent construction porphyrinoid would provide opportunities developing new materials optoelectronic applications.