Siloxy Group-Induced Highly Efficient Room Temperature Phosphorescence with Long Lifetime

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• 作者：Masaki Shimizu ; Ryosuke Shigitani ; Masaki Nakatani ; Keiko Kuwabara ; Yusuke Miyake ; Kunihiko Tajima ; Hayato Sakai ; Taku Hasobe
• 刊名：Journal of Physical Chemistry C
• 出版年：2016
• 出版时间：June 2, 2016
• 年：2016
• 卷：120
• 期：21
• 页码：11631-11639
• 全文大小：482K
• 年卷期：0
• ISSN：1932-7455

文摘

The design and development of organic phosphors that exhibit efficient emission at room temperature but do not contain precious metals such as iridium and platinum have attracted increasing attention. We report herein highly efficient green phosphorescence-emitting 1,4-dibenzoyl-2,5-bis(siloxy)benzene crystals in air at room temperature. Remarkable luminescence quantum yields of 0.46 to 0.64 and long lifetimes ranging from 76.0 to 98.3 ms were observed. X-ray diffraction analysis of the single crystals revealed that there were several intermolecular interactions causing suppression of intramolecular motion, thereby minimizing nonradiative decay of the triplet excited state. Comparison with the corresponding 2,5-bis(dimethylphenylsilylmethyl) and 2,5-bis(trimethylsilyl) derivatives revealed that the siloxy groups are essential for efficient room temperature phosphorescence. Density functional calculations suggested that σ–n conjugation was operative in the siloxy moieties. Electron spin resonance measurement indicated that the radiative process included generation of the triplet diradical species, whose electron distribution was very similar to that of naphthalene. The present study largely expands the possibilities for the molecular design of precious metal- and halogen-free organic phosphors exhibiting efficient room temperature phosphorescence.