Citation:
WANG Feng-Jiao, ZHOU Dan-Hong, ZUO Shi-Ying, CAO Jian-Fang, PENG Xiao-Jun. Theoretical Calculations on the PET Property of BODIPY Fluorescent pH Probes[J]. Acta Physico-Chimica Sinica,
;2012, 28(07): 1645-1650.
doi:
10.3866/PKU.WHXB201205083
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4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) fluorescent pH probes are fluorescent sensors and switchers based on photo-induced electron transfer (PET) mechanism. From experimental studies, different substituents on the amino nitrogen are known to result in variable photo sensitivities. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations are used to optimize the structures of six different BODIPY probe molecules with different substituted amines, and to study their exited states. In the ground state, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the probe molecules are located on the π and π* orbitals of the BODIPY dye, and the lone pair electrons from the amino nitrogen form the HOMO-1 orbital. In the first exited state, for the probes with two substituent groups on the amino nitrogen, the HOMO-1→ LUMO transition has a smaller emission energy than that of the HOMO→LUMO transition in the BODIPY host, which may induce the PET effect and quench the fluorescence. After the geometry optimization of the exited states, irrespective of whether one or two groups are linked on the amino nitrogen, the orbital symmetry of the nitrogen atom changes from sp3→sp2, and the lone pair electrons occupy the p orbital situated between the HOMO and LUMO of BODIPY, resulting in the PET effect. The calculated results are in od agreement with the experimental results.
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