Probing the molecular and electronic structure of the lichen metabolite usnic acid: A DFT study

被引:16
|
作者
Galasso, V. [1 ]
机构
[1] Univ Trieste, Dipartimento Sci Chim, I-34127 Trieste, Italy
关键词
DFT calculations; Structure; Vibrational frequencies; NMR chemical shifts; Absorption spectrum; HYDROGEN-BOND; SPECTRA; CARBONYL; SOLVENT; DEACTIVATION; DERIVATIVES; ABSORPTION; BEHAVIOR; JUGLONE; SHIFTS;
D O I
10.1016/j.chemphys.2010.07.017
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The molecular structure of usnic acid was investigated by the density functional theory (DFT). Two keto-enol tautomers are nearly isoenergetic and more stable than other tautomers. Noteworthy is the energy difference among the three intramolecular O-H center dot center dot center dot O hydrogen bonds. The DFT/PCM calculated dissociation constants account for the acidic sequence of the three OH-groups. The electronic structure was also studied by calculating IR/Raman, NMR, and absorption features. A reliable assignment of the 'fingerprint' carbonyl stretching modes was supported by calculations on related molecules. The calculated NMR chemical shifts fit expectation in terms of a fast interconversion between the two most preferred tautomers. A variety of pi -> pi* and n -> pi* excitations, localized on a single ring or involving a charge-transfer between the two lateral rings of the molecule, gives rise to the broad UV-absorption bands. This property accounts for the efficient protection against damaging solar radiation provided by usnic acid for lichens. (C) 2010 Elsevier B.V. All rights reserved.
引用
收藏
页码:138 / 145
页数:8
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