Combined Experimental and Theoretical Study of the Transient IR Spectroscopy of 7-Hydroxyquinoline in the First Electronically Excited Singlet State

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• 作者：Felix Hoffmann ; Maria Ekimova ; Gül Bekçioğlu-Neff ; Erik T. J. Nibbering ; Daniel Sebastiani
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：December 1, 2016
• 年：2016
• 卷：120
• 期：47
• 页码：9378-9389
• 全文大小：666K
• ISSN：1520-5215

文摘

The photophysics of 7-hydroxyquinoline (7HQ) in protic media results from an interplay of acid–base chemistry, prompted by the effects of photoacidity of the hydroxyl group and photobasicity of the nitrogen atom in the quinoline aromatic system. With ultrafast IR spectroscopic measurements, we follow the proton transfer dynamics of 7HQ in its four possible charged forms in methanol solution. Using deuterated methanol as solvent, we determine deuteron transfer rates from the neutral to the zwitterionic form to be 330 ps, those from the cationic form to the zwitterionic form to be 170 ps, and those from the anionic form to the zwitterionic form to be 600 ps. We compare the observed IR-active fingerprint marker patterns in the electronic ground state and the first electronically excited ¹L_b-state with those calculated using density functional theory and time-dependent density functional theory, respectively, and find good correspondence between experimental and calculated transitions. The calculations provide insight into the nature of electronic excitation of these four different charged forms of 7HQ, suggesting the key role of electronic charge distribution changes upon electronic excitation of 7HQ and hydrogen bond changes at the donor hydroxyl and acceptor nitrogen moieties.