A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals

Shun Kimura, Shojiro Kimura, Ken Kato, Yoshio Teki, Hiroshi Nishihara, Tetsuro Kusamoto

Research output: Contribution to journalArticlepeer-review

Abstract

Organic radicals are an emerging class of luminophores possessing multiplet spin states and potentially showing spin-luminescence correlated properties. We investigated the mechanism of recently reported magnetic field sensitivity in the emission of a photostable luminescent radical, (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM) doped into hostαH-PyBTM molecular crystals. The magnetic field (0-14 T), temperature (4.2-20 K), and the doping concentration (0.1, 4, 10, and 22 wt%) dependence on the time-resolved emission were examined by measuring emission decays of the monomer and excimer. Quantum mechanical simulations on the decay curves disclosed the role of the magnetic field; it dominantly affects the spin sublevel population of radical dimers in the ground states. This situation is distinctly different from that in conventional closed-shell luminophores, where the magnetic field modulates their excited-state spin multiplicity. Namely, the spin degree of freedom of ground-state open-shell molecules is a new key for achieving magnetic-field-controlled molecular photofunctions.

Original languageEnglish
Pages (from-to)2025-2029
Number of pages5
JournalChemical Science
Volume12
Issue number6
DOIs
Publication statusPublished - 14 Feb 2021

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