Collect. Czech. Chem. Commun.
1995, 60, 1621-1633
https://doi.org/10.1135/cccc19951621
Photocolouration of 2,4,4,6-Tetraaryl-4H-pyrans and Their Heteroanalogues: Importance of Hypervalent Photoisomers
Stanislav Böhma, Mojmír Adamecb, Stanislav Nešpůrekb and Josef Kuthana
a Department of Organic Chemistry,Prague Institute of Chemical Technology, 166 28 Prague 6, Czech Republic
b Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6, Czech Republic
Abstract
Molecular geometries of 2,4,4,6-tetraphenyl-4H-pyran (Ia), 4,4-(biphenyl-2,2e-diyl)-2,6-diphenyl-4H-pyran (Ib) and their heterocyclic isomers II-V were optimized by the PM3 method and used for the calculation of electronic absorption spectra by the CNDO/S-CI procedure. Comparison of the theoretical data with experimental UV-VIS absorption spectra made possible to select hypervalent molecules IIIa, IIIb, IVa and IVb being responsible for the photocolouration of 4H-pyrans Ia, Ib, while compounds Va, Vb, VI and VII come into account as possible photodegradation products. The bleaching process of the UV illuminated compound Ia is analyzed in terms of dispersive first-order reaction kinetics.
