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 journalArticle

3 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

Fingerprint

Energy Transfer
Porphyrins
Energy transfer
Isomers
Halogenation
Excitation energy
Electrochemical properties
Optoelectronic devices
Catalytic Domain
Spectrum Analysis
Optical properties
Spectroscopy
Zinc

All Science Journal Classification (ASJC) codes

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

Cite this

Li, Qizhao ; Li, Chengjie ; Kim, Jinseok ; Ishida, Masatoshi ; Li, Xin ; Gu, Tingting ; Liang, Xu ; Zhu, Weihua ; Ågren, Hans ; Kim, Dongho ; Furuta, Hiroyuki ; Xie, Yongshu. / Regioselectively Halogenated Expanded Porphyrinoids as Building Blocks for Constructing Porphyrin-Porphyrinoid Heterodyads with Tunable Energy Transfer. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 13. pp. 5294-5302.
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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 F{\"o}rster-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.",
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Regioselectively Halogenated Expanded Porphyrinoids as Building Blocks for Constructing Porphyrin-Porphyrinoid Heterodyads with Tunable Energy Transfer. / Li, Qizhao; Li, Chengjie; Kim, Jinseok; Ishida, Masatoshi; Li, Xin; Gu, Tingting; Liang, Xu; Zhu, Weihua; Ågren, Hans; Kim, Dongho; Furuta, Hiroyuki; Xie, Yongshu.

In: Journal of the American Chemical Society, Vol. 141, No. 13, 03.04.2019, p. 5294-5302.

Research output: Contribution to journalArticle

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T1 - Regioselectively Halogenated Expanded Porphyrinoids as Building Blocks for Constructing Porphyrin-Porphyrinoid Heterodyads with Tunable Energy Transfer

AU - Li, Qizhao

AU - Li, Chengjie

AU - Kim, Jinseok

AU - Ishida, Masatoshi

AU - Li, Xin

AU - Gu, Tingting

AU - Liang, Xu

AU - Zhu, Weihua

AU - Ågren, Hans

AU - Kim, Dongho

AU - Furuta, Hiroyuki

AU - Xie, Yongshu

PY - 2019/4/3

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AB - 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.

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