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Origin of intersystem crossing in highly distorted organic molecules: a case study with red light-absorbing N,N,O,O-boron-chelated Bodipys

Lookup NU author(s): Emeritus Professor Anthony Harriman



This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).


© 2023 The Royal Society of Chemistry.To explore the relationship between the twisted π-conjugation framework of aromatic chromophores and the efficacy of intersystem crossing (ISC), we have studied a N,N,O,O-boron-chelated Bodipy derivative possessing a severely distorted molecular structure. Surprisingly, this chromophore is highly fluorescent, showing inefficient ISC (singlet oxygen quantum yield, ΦΔ = 12%). These features differ from those of helical aromatic hydrocarbons, where the twisted framework promotes ISC. We attribute the inefficient ISC to a large singlet-triplet energy gap (ΔES1/T1 = 0.61 eV). This postulate is tested by critical examination of a distorted Bodipy having an anthryl unit at the meso-position, for which ΦΔ is increased to 40%. The improved ISC yield is rationalized by the presence of a T2 state, localized on the anthryl unit, with energy close to that of the S1 state. The electron spin polarization phase pattern of the triplet state is (e, e, e, a, a, a), with the Tz sublevel of the T1 state overpopulated. The small zero-field splitting D parameter (−1470 MHz) indicates that the electron spin density is delocalized over the twisted framework. It is concluded that twisting of π-conjugation framework does not necessarily induce ISC, but S1/Tn energy matching may be a generic feature for increasing ISC for a new-generation of heavy atom-free triplet photosensitizers.

Publication metadata

Author(s): Zhang X, Sukhanov AA, Liu X, Taddei M, Zhao J, Harriman A, Voronkova VK, Wan Y, Dick B, Di Donato M

Publication type: Article

Publication status: Published

Journal: Chemical Science

Year: 2023

Pages: epub ahead of print

Online publication date: 15/04/2023

Acceptance date: 14/04/2023

Date deposited: 16/05/2023

ISSN (print): 2041-6520

ISSN (electronic): 2041-6539

Publisher: Royal Society of Chemistry


DOI: 10.1039/d3sc00854a


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