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Tuning the Solid‐State Luminescence of BODIPY Derivatives with Bulky Arylsilyl Groups: Synthesis and Spectroscopic Properties
Author(s) -
Lu Hua,
Wang Qiuhong,
Gai Lizhi,
Li Zhifang,
Deng Yuan,
Xiao Xuqiong,
Lai Guoqiao,
Shen Zhen
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201200169
Subject(s) - bodipy , sonogashira coupling , chemistry , fluorescence , stacking , photochemistry , luminescence , chromophore , pyrrole , molecule , intermolecular force , solid state , crystallography , materials science , organic chemistry , palladium , physics , optoelectronics , quantum mechanics , catalysis
Boron dipyrromethenes (BODIPYs) with bulky triphenylsilylphenyl(ethynyl) and triphenylsilylphenyl substituents on pyrrole sites were prepared via Hagihara–Sonogashira and Suzuki–Miyaura cross‐coupling with ethynyl‐terminated tetraphenylsilane and boronic acid‐terminated tetraphenylsilane. The chromophores are designed to prevent intermolecular π–π stacking interaction and enhance fluorescence in the solid state. Single crystals of 1 a and 2 b for X‐ray structural analysis were obtained, and weak π–π stacking interactions of the neighboring BODIPY molecules were observed. Spectroscopic properties of all of the dyes in various solvents and in films were investigated. Triphenylsilylphenyl‐substituted BODIPYs generally show more pronounced increases in solid‐state emission than triphenylsilylphenyl(ethynyl)‐substituted BODIPYs. Although the simple BODIPYs do not exhibit any fluorescence in the solid state ( Φ =0), arylsilyl‐substituted BODIPYs exhibit weak to moderate solid‐state fluorescence with quantum yields of 0.03, 0.07, 0.10, and 0.25. The structure–property relationships were analyzed on the basis of X‐ray crystallography, optical spectroscopy, cyclic voltammetry, and theoretical calculations.