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Key of Suppressed Triplet Nonradiative Transition-Dependent Chemical Backbone for Spatial Self-Tunable Afterglow
Author(s) -
Indranil Bhattacharjee,
Kikuya Hayashi,
Shuzo Hirata
Publication year - 2021
Publication title -
jacs au
Language(s) - English
Resource type - Journals
ISSN - 2691-3704
DOI - 10.1021/jacsau.1c00132
Subject(s) - chromophore , phosphorescence , coronene , excited state , quantum yield , photochemistry , afterglow , chemistry , yield (engineering) , ground state , excitation , materials science , atomic physics , molecule , fluorescence , optics , organic chemistry , physics , electrical engineering , gamma ray burst , astronomy , metallurgy , engineering
Highly efficient persistent (lifetime > 0.1 s) room-temperature phosphorescence ( p RTP) chromophores are important for futuristic high-resolution afterglow imaging for state-of-the-art security, analytical, and bioimaging applications. Suppression of the radiationless transition from the lowest triplet excited state (T 1 ) of the chromophores is a critical factor to access the high RTP yield and RTP lifetime for desirable p RTP. Logical explanations for factor suppression based on chemical structures have not been reported. Here we clarify a strategy to reduce the radiationless transition from T 1 based on chemical backbones and yield a simultaneous high RTP yield and high RTP lifetime. Yellow phosphorescence chromophores that contain a coronene backbone were synthesized and compared with yellow phosphorescent naphthalene. One of the designed coronene derivatives reached a RTP yield of 35%, which is the best value for chromophores with a RTP lifetime of 2 s. The optically measured rate constant of a radiationless transition from T 1 was correlated precisely with a multiplication of vibrational spin-orbit coupling (SOC) at a T 1 geometry and with the Franck-Condon chromophore factor. The agreement between the experimental and theoretical results confirmed that the extended two-dimensional fused structure in the coronene backbone contributes to a decrease in vibrational SOC and Franck-Condon factor between T 1 and the ground state to decrease the radiationless transition. A resolution-tunable afterglow that depends on excitation intensity for anticounterfeit technology was demonstrated, and the resultant chromophores with a high RTP yield and high RTP lifetime were ideal for largely changing the resolution using weak excitation light.

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