NDLI: Constraint-induced structural deformation of planarized triphenylboranes in the excited state

Content Provider	Royal Society of Chemistry (RSC)
Author	Irle, Stephan Muramatsu, Masayasu Nagasawa, Yutaka Miyasaka, Hiroshi Wakamiya, Atsushi Kitamura, Noboru Camacho, Cristopher Katayama, Tetsuro Shuto, Ayumi Zhou, Zhiguo Yamaguchi, Shigehiro Ito, Syoji Sakuda, Eri Kushida, Tomokatsu
Copyright Year	2014
Abstract	Triphenylboranes planarized with three methylene bridges exhibited dual fluorescence bands around 340 and 400 nm despite their structural constraint. To elucidate the origin, their excited state dynamics were experimentally and theoretically studied. The measurements of fluorescence lifetimes and transient absorption spectra indicated that the planarized triphenylboranes adopt two local minimum structures in the lowest-energy excited singlet (S1) state. The TD-DFT potential energy surface of the S1 state possesses at least two minimum energy structures associated with a planar and a bowl-shaped molecular structure. The theoretical S1–S0 transition energies at these geometries were in good agreement with the experimentally observed values. These results indicated that the plane-to-bowl structural relaxation in the S1 state is the origin of the dual fluorescence. Based on the calculated partial atomic charge on the boron atom, the structural deformation to the bowl-shaped structure results in an increase in the electron density on the boron center. Thus, the enhanced intramolecular charge-transfer character plays a role in this structural deformation. Similar behavior was also observed for trigonally π-expanded planarized borane derivatives. These results provide an important implication that structural constraint in a planar fashion is not only a strategy to construct a rigid skeleton, but also a viable mechanism to impart flexibility to the skeleton.
Starting Page	1296
Ending Page	1304
Page Count	9
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	5
Issue Number	4
Journal	Chemical Science
DOI	10.1039/c3sc52751d
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Potential energy surface Boron Methylene bridge Fluorescence Maxima and minima
Content Type	Text
Resource Type	Article
Subject	Chemistry

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