Photophysics of (1-Butyl-4-(1H-inden-1-ylidene)-1,4-dihydropyridine (BIDP): An Experimental Test for Conical Intersections
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- 作者：Semyon Cogan ; Anat Kahan ; Shmuel Zilberg ; Yehuda Haas
- 刊名：Journal of Physical Chemistry A
- 出版年：2008
- 出版时间：June 26, 2008
- 年：2008
- 卷：112
- 期：25
- 页码：5604 - 5612
- 全文大小：321K
- 年卷期：v.112,no.25(June 26, 2008)
- ISSN：1520-5215
文摘
Fluorescence experiments on (1-butyl-4-(1H-inden-1-ylidene)-1,4-dihydropyridine (BIDP) are reported in liquid and glassy solutions. The data indicate a fast decay in the fluid nonpolar, nonprotic solutions (decay times ~10−12 s) and rapid but considerably slower decay in polar ones. In frozen solutions (polar and nonpolar), the fluorescence quantum yield is much higher (near 0.5 and around 0.1 in polar and nonpolar glasses, respectively). The rapid nonradiative transitions in fluid solutions are assigned to internal conversion in both solvent classes, as intersystem crossing is much slower and no net reaction is observed. These results are in agreement with predictions made for the closely related (in terms of electronic structure) but simpler molecule cyclopentadienyl-1,4-dihydropyridine (CPDHP) for which an S1/S0 conical intersection was recently proposed [Int. J. Quant. Chem. 2005, 102, 961]. The crossing of the two lowest singlet states is calculated to vanish in polar solvents such as methyl cyanide, leading to longer lifetime of S1 of CPDHP. As BIDP has a very similar electronic structure, the model predicts a corresponding change in this larger molecule. The strong fluorescence observed in the glassy environments is rationalized by the hindering of the internal torsion required to reach the geometry of the conical intersection.