Temperature-Induced Sign Inversion of Circularly Polarized Luminescence of Binaphthyl-Bridged Tetrathiapyrenophanes

Kazuto Takaishi; Fumiya Yoshinami; Yoshihiro Sato; Tadashi Ema

doi:10.1002/chem.202400866

Temperature-Induced Sign Inversion of Circularly Polarized Luminescence of Binaphthyl-Bridged Tetrathiapyrenophanes

Chemistry. 2024 Apr 3:e202400866. doi: 10.1002/chem.202400866. Online ahead of print.

Authors

Kazuto Takaishi¹, Fumiya Yoshinami¹, Yoshihiro Sato¹, Tadashi Ema¹

Affiliation

¹ Division of Applied Chemistry, Graduate School of Environmental, Life, Natural Science and Technology, Okayama University, Tsushima, Okayama, 700-8530, Japan.

PMID: 38567834
DOI: 10.1002/chem.202400866

Abstract

D₂-symmetric (R)-binaphthyl-bridged pyrenophanes containing thioether bonds were synthesized. The pyrenophanes exhibited the temperature-induced sign inversion of circularly polarized luminescence (CPL) while maintaining the emission wavelength and reversibility. The Δg_lum value reached 0.02, and the FL quenching by heat was negligible. The sign inversion of CPL originates from the inversion of intramolecular excimer chirality associated with excitation dynamics. The two pyrenes form a kinetically trapped left-handed twist excimer at low temperatures, while they form a thermodynamically favored right-handed twist excimer at high temperatures. The thioether linkers can impart flexibility suitable for the inversion of chirality of the excimers.

Keywords: Biaryls; Circularly polarized luminescence; Conformation analysis; Excimers; Thermo-driven switches.

Abstract

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