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Excited state intramolecular proton transfer in 2-(2′-amino-3-pyridyl)-benzimidazole: effect of solvents
Excited state intramolecular proton transfer (ESIPT) has been studied in 2-(2′-amino-3-pyridyl)benzimidazole (2-A3PyBI) in different solvents with the help of absorption, fluorescence excitation and fluorescence spectroscopy and time resolved emission spectrofluorimetry. Electronic structure calcula...
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Published in: | Chemical physics 2004-10, Vol.305 (1), p.95-103 |
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Main Authors: | , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | Excited state intramolecular proton transfer (ESIPT) has been studied in 2-(2′-amino-3-pyridyl)benzimidazole (2-A3PyBI) in different solvents with the help of absorption, fluorescence excitation and fluorescence spectroscopy and time resolved emission spectrofluorimetry. Electronic structure calculations on each species were carried out using semi-empirical AM1 method and hybrid density functional theory (DFT) B3LYP using 6-31 G∗∗ basis set and Gaussian 98 program. Dual fluorescence is observed in all the solvents. Based on theoretical and experimental results, normal small Stokes shifted emission is assigned to rotamer a-2 in non-polar solvents and a-3 in polar protic solvents. Long wavelength (LW) and large Stokes shifted band is due to tautomer formed by ESIPT from rotamer a-1. Presence of electron withdrawing
N-atom
ortho to –NH
2 group increases its acidity. Due to this rate of ESIPT process will be enhanced and thus the fluorescence quantum yield
(
Φ
f
T
)
of the tautomer will also be increased. Both AM1 and DFT calculations have shown that a-1 is the most stable among all the rotamers and semi-empirical calculations have indicated that the activation barrier for interconvertion of a-1 to a-2 is only 2.6 kJ
mol
−1 in the ground state (S
0) and 44.3 kJ
mol
−1 in the first excited singlet (S
1). On the other hand, activation barrier height for the conversion of a-1 to a-T is 132 kJ
mol
−1 in S
0 state and 72 kJ
mol
−1 in S
1 state, obtained by AM1 method. |
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ISSN: | 0301-0104 |
DOI: | 10.1016/j.chemphys.2004.06.037 |