Triplet–Triplet Annihilation Upconversion Circularly Polarized Luminescence That Originates From Achiral and Racemic Luminophores Encapsulated in Chiral Silica
Abstract
ABSTRACT Circularly polarized luminescence (CPL) has emerged as a key optical property with chiral‐photonic and optoelectronic applications. However, conventional CPL systems rely on synthetically demanding chiral luminophores that emit at fixed wavelengths, which limits tunability and efficiency. In this study, we demonstrate that achiral or racemic luminophores co‐encapsulated with photosensitizers in the helical nanocavities of chiral silica exhibit upconversion CPL (UC‐CPL). The chiral silica, which is derived from polymethylvinylsiloxane comprising polyhedral oligomeric silsesquioxane decorated with enantiomeric N ‐( tert ‐butoxycarbonyl)cysteine methyl ester moieties (PMVS‐POSS‐Cys), has a helical structure with a preferred‐handedness that facilitates efficient triplet–triplet energy transfer (TTET) and triplet–triplet annihilation (TTA). The resulting materials exhibit distinct CPL and UC‐CPL signals when excited at 365 and 532 nm, respectively, despite the achiral nature of the luminophore. This study unprecedentedly demonstrates UC‐CPL from achiral emitters within chiral silica matrices, which is achieved through chiral induction in the solid‐state helical silica frameworks. The strategy described herein provides a general and versatile platform for developing energy‐efficient, wavelength‐tunable chiral‐photonic materials without the need for elaborate chiral syntheses.
Article Details
Authors (17)
Shunsuke Morii
Department of Applied Chemistry Faculty of Engineering and Graduate School of Engineering Osaka Institute of Technology Osaka Japan
Himawari Kunitake
Department of Applied Chemistry Faculty of Engineering and Graduate School of Engineering Osaka Institute of Technology Osaka Japan
Yasumasa Miyoshi
Department of Applied Chemistry Faculty of Engineering and Graduate School of Engineering Osaka Institute of Technology Osaka Japan
Shinichi Kusaka
Department of Applied Chemistry Faculty of Engineering and Graduate School of Engineering Osaka Institute of Technology Osaka Japan
Towa Shinoda
Department of Applied Chemistry Faculty of Engineering and Graduate School of Engineering Osaka Institute of Technology Osaka Japan
Kai Terami
Department of Applied Chemistry Faculty of Engineering and Graduate School of Engineering Osaka Institute of Technology Osaka Japan
Yu‐Hsuan Chan
Department of Biological Science and Technology Center For Intelligent Drug Systems and Smart Bio‐Devices (IDS2B) National Yang Ming Chiao Tung University Hsinchu Taiwan
Yi‐Ting Lin
Department of Biological Science and Technology Center For Intelligent Drug Systems and Smart Bio‐Devices (IDS2B) National Yang Ming Chiao Tung University Hsinchu Taiwan
Hao‐Cheng Yu
Department of Biological Science and Technology Center For Intelligent Drug Systems and Smart Bio‐Devices (IDS2B) National Yang Ming Chiao Tung University Hsinchu Taiwan
Syuji Fujii
Yoshinobu Nakamura
Yoshiro Kaneko
Teruaki Hayakawa
Department of Materials Science and Engineering, School of Materials and Chemical Technology Institute of Science Tokyo Meguro‐ku Tokyo Japan
Tatsuo Nakagawa
UNISOKU Co, Ltd. Hirakata Osaka Japan
Hiroaki Hanada
UNISOKU Co, Ltd. Hirakata Osaka Japan
Ming‐Chia Li
Department of Biological Science and Technology Center For Intelligent Drug Systems and Smart Bio‐Devices (IDS2B) National Yang Ming Chiao Tung University Hsinchu Taiwan
Tomoyasu Hirai
Department of Applied Chemistry Faculty of Engineering and Graduate School of Engineering Osaka Institute of Technology Osaka Japan