Regioselectively Halogenated Expanded Porphyrinoids as Building Blocks for Constructing Porphyrin–Porphyrinoid Heterodyads with Tunable Energy Transfer LiQizhao LiChengjie KimJinseok IshidaMasatoshi LiXin GuTingting LiangXu ZhuWeihua ÅgrenHans KimDongho FurutaHiroyuki XieYongshu 2019 Expanded porphyrins have been attracting increasing attention owing to their unique optical and electrochemical properties as well as switchable aromaticity. Toward material applications, regioselective functionalization of the expanded porphyrins at their periphery is indeed challenging due to the presence of multiple reactive sites. Herein, a set of regioselective halogenated isomers (<b>L5-Br-A/B/C</b>) of neo-confused isosmaragdyrin (<b>L5</b>) are synthesized by a combination of the halogenation reaction of <b>L5</b> and sequential macrocycle-to-macrocycle transformation reactions of its halogenated isomers. On this basis, the regioselectively functionalized isosmaragdyrins are utilized as building blocks for constructing multichromophoric porphyrinoids, specifically, heterodyads <b>L5-ZnP-A/B/C</b>, in which a common zinc porphyrin is linked at three different pyrrolic positions of isosmaragdyrins, respectively, by Sonogashira coupling reactions. The highly efficient energy cascade from porphyrin to isosmaragdyrin is elucidated using steady-state/time-resolved spectroscopies and theoretical calculations. Notably, the energy transfer processes from the porphyrin to the isosmaragdyrin moieties as well as the excitation energy transfer rates in <b>L5-ZnP-A/B/C</b> are highly dependent on the linking sites by through-bond and Förster-type resonance energy transfer mechanisms. The site-selective functionalization and subsequent construction of a set of heterodyads of the expanded porphyrinoid would provide opportunities for developing new materials for optoelectronic applications.