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Theoretical Study of the Electronic Excited States and Fluorescence Spectra of Squaraine in Solution

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An Erratum to this article was published on 17 October 2014

Abstract

Bis[4-(dimethylamino)phenyl]squaraine (SQ-DMA) has been used as a long wavelength fluorescence dye. In spite of various experimental and theoretical studies, its excited state properties and the relaxation mechanism have not been elucidated. In this work, we tried to clarify these points from a theoretical point of view. The heats of reaction from the planar to possible twisted conformers in the first excited state S1 in solvents were calculated to be significantly endothermic, thus the twisted structures turn out to be less important, which contradicts earlier proposals made in experimental studies. This behavior is in a sharp contrast with that of the related molecule 4-(N,N-dimethylamino)benzonitrile, and is explained by the difference in their electronic characters of their relevant excited states; the S1 state of SQ-DMA is a simple HOMO-to-LUMO excited state with a delocalized character. Furthermore, the theoretically simulated absorption and fluorescence spectra with the planar structure of SQ-DMA are in good agreement with the corresponding experimental results. These results suggest that the responsible S1 state is the lowest 1B1u state with a planar D2h structure.

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Acknowledgments

The authors acknowledge Prof. Koji Suzuki and Dr. Keitaro Umezawa of Keio University for having suggested this theoretical study on SQ-DMA. This work was supported by Grants-in-Aid for Scientific Research funded by MEXT in Japan, and by the MEXT-Supported Program for the Strategic Research Foundation at Private Universities, 2009–2013. The computations were partly carried out using the computer facilities at the Research Center for Computational Science, Okazaki National Institutes.

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  1. Department of Chemistry Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, 223-8522, Japan

    Hitoshi Ozawa, Kazunori Yashiro, Takuma Yamamoto & Satoshi Yabushita

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  1. Hitoshi Ozawa
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  2. Kazunori Yashiro
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  3. Takuma Yamamoto
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Correspondence to Satoshi Yabushita.

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Ozawa, H., Yashiro, K., Yamamoto, T. et al. Theoretical Study of the Electronic Excited States and Fluorescence Spectra of Squaraine in Solution. J Solution Chem 43, 1625–1643 (2014). https://doi.org/10.1007/s10953-014-0224-x

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