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 shu

Theoretical Calculations on the PET Property of BODIPY Fluorescent pH Probes

1.
1. Institute of Chemistry for Functionalized Materials, College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China;
2. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, Liaoning Province, P. R. China

Received Date: 17 March 2012
Available Online: 8 May 2012
Fund Project: 精细化工国家重点实验室(大连理工大学)开放课题基金(KF0907)资助项目 (大连理工大学)开放课题基金(KF0907)

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.
- Time-dependent density functional theory,
- BODIPY dye,
- pH fluorescent probe,
- Photo-induced electron transfer
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