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

Qizhao Li, Chengjie Li, Jinseok Kim, Masatoshi Ishida, Xin Li, Tingting Gu, Xu Liang, Weihua Zhu, Hans Ågren, Dongho Kim, Hiroyuki Furuta, Yongshu Xie

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)

Abstract

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 (L5-Br-A/B/C) of neo-confused isosmaragdyrin (L5) are synthesized by a combination of the halogenation reaction of L5 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 L5-ZnP-A/B/C, 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 L5-ZnP-A/B/C 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.

Original languageEnglish
Pages (from-to)5294-5302
Number of pages9
JournalJournal of the American Chemical Society
Volume141
Issue number13
DOIs
Publication statusPublished - 2019 Apr 3

Bibliographical note

Funding Information:
This work at ECUST was financially supported by Shanghai Municipal Science and Technology Major Project (Grant No. 2018SHZDZX03) and the international cooperation program of Shanghai Science and Technology Committee (17520750100), NSFC (21772041, 21702062 21811530005), the Program for Professor of Special Appointment (Eastern Scholar, GZ2016006) at Shanghai Institutions of Higher Learning, Shanghai Pujiang Program (17PJ1401700), the Fundamental Research Funds for the Central Universities (WK1616004, 222201717003), and Program of Introducing Talents of Discipline to Universities (B160170). Part of the work in Kyushu was supported by Grants-in-Aid (JP15K13646 to H.F., JP16K05700 and JP17H05377 to M.I.) from the Japan Society for the Promotion of Science (JSPS). The work at Yonsei was supported by the Global Research Laboratory (GRL) Program funded by the Ministry of Science, ICT & Future, Korea (2013K1A1A2A02050183). The authors thank Research Center of Analysis and Test of East China University of Science and Technology for the help on the characterization.

Funding Information:
This work at ECUST was financially supported by Shanghai Municipal Science and Technology Major Project (Grant No. 2018SHZDZX03) and the international cooperation program of Shanghai Science and Technology Committee (17520750100), NSFC (21772041, 21702062, 21811530005), the Program for Professor of Special Appointment (Eastern Scholar, GZ2016006) at Shanghai Institutions of Higher Learning, Shanghai Pujiang Program (17PJ1401700), the Fundamental Research Funds for the Central Universities (WK1616004, 222201717003), and Program of Introducing Talents of Discipline to Universities (B160170). Part of the work in Kyushu was supported by Grants-in-Aid (JP15K13646 to H.F., JP16K05700 and JP17H05377 to M.I.) from the Japan Society for the Promotion of Science (JSPS). The work at Yonsei was supported by the Global Research Laboratory (GRL) Program funded by the Ministry of Science, ICT & Future, Korea (2013K1A1A2A02050183). The authors thank Research Center of Analysis and Test of East China University of Science and Technology for the help on the characterization.

Publisher Copyright:
© 2019 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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