ISSN:
0009-2940
Keywords:
Conformations, solid state
;
Conformers in solution
;
UV-Vis transition energies and CO/CO dihedral angles
;
CO/CO rotational barriers
;
Calculations, CNDO/S-CI, MMP1, PIMM / PE spectroscopy
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Chromophoric Systems, 2. - Conformation and Absorption of Light in (2-Alkoxyvinyl)ethanedionesThe unusual color properties of yellow 1,2-bis(4,5-dihydrofuran-3-yl)ethane-1,2-dione (1) and colorless 1,2-bis(5,6-dihydro-4H-pyran-3-yl)ethane-1,2-dione (2) in the solid state and in solution are investigated by crystal structure analysis, UV-Vis, PE, and 13C-NMR spectroscopy as well as by reparameterized force-field calculations. Dione 1 takes an antiperiplaner CO/CO conformation of its chromophore in the solid state whereas dione 2 is twisted in this respect by 102°. In solution both chromophores are not planar, but 1 is less distorted (ca. 142°) than dione 2 (ca. 126°). The calculated rotational barrier for CO/CO twisting amounts to 0.9 kcal mol-1 for 1 and to 2.2 kcal mol-1 for 2.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240424
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