Visible Absorption and Fluorescence Spectroscopy of Conformationally Constrained, Annulated BODIPY Dyes

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• 作者：No毛l Boens ; Volker Leen ; Wim Dehaen ; Lina Wang ; Koen Robeyns ; Wenwu Qin ; Xiaoliang Tang ; David Beljonne ; Claire Tonnel茅 ; Jose M. Paredes ; Maria J. Ruedas-Rama ; Angel Orte ; Luis Crovetto ; Eva M. Talavera ; Jose M. Alvarez-Pez
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：October 4, 2012
• 年：2012
• 卷：116
• 期：39
• 页码：9621-9631
• 全文大小：513K
• 年卷期：v.116,no.39(October 4, 2012)
• ISSN：1520-5215

文摘

Six conformationally restricted BODIPY dyes with fused carbocycles were synthesized to study the effect of conformational mobility on their visible electronic absorption and fluorescence properties. The symmetrically disubstituted compounds (2, 6) have bathochromically shifted absorption and fluorescence spectral maxima compared to those of the respective asymmetrically monosubstituted dyes (1, 5). Fusion of conjugation extending rings to the 伪,尾-positions of the BODIPY core is an especially effective method for the construction of boron dipyrromethene dyes absorbing and emitting at longer wavelengths. The fluorescence quantum yields 桅 of dyes 1鈥?b>6 are high (0.7 鈮?桅 鈮?1.0). The experimental results are backed up by quantum chemical calculations of the lowest electronic excitations in 1, 2, 5, 6, and corresponding dyes of related chemical structure but without conformational restriction. The effect of the molecular structure on the visible absorption and fluorescence emission properties of 1鈥?b>6 has been examined as a function of solvent by means of the recent, generalized treatment of the solvent effect, proposed by Catal谩n (J. Phys. Chem. B2009, 113, 5951鈥?960). Solvent polarizability is the primary factor responsible for the small solvent-dependent shifts of the visible absorption and fluorescence emission bands of these dyes.