1π→1π Ultraviolet Absorption Bands and Electronic Charge Transfers in Singlet Excited States of Sulfur Aromatic Heterocycles

• Published in: Spectroscopy letters 2005-07, Vol.38 (4-5), p.605-616
• Main Authors: Araya, Carmen G., Vargas, Víctor, Morales, Raúl G. E.
• Format: Article
• Language: English
• Subjects: Ab initio, AM1 and INDO; electronic absorption bands; S-CIS molecular orbital calculations; sulfur heterocycles
• ISSN: 0038-7010; 1532-2289
• DOI: 10.1081/SL-200062847

Indoline-2-thione (BC), benzimidazole-2-thione (BN), benzoxazole-2-thione (BO), and benzothiazole-2-thione (BS) define an interesting series of aromatic compounds containing a NCS synthonic unit in a heterocyclic ring of five centers, substituted by atomic centers of the type C, N, O, or S, where the main electronic absorption bands are localized in the spectral range of ultraviolet A or B. The first two singlet electronic transitions of this series, 1 S 0 → 1 S 1 (n,π*) and 1 S 0 → 1 S 2 (π,π*), determine the main spectroscopic characteristic of these compounds in order to be used as potential photochemical actinometers of solar ultraviolet radiation. Furthermore, the second electronic transition, localized in the 270-360 nm ultraviolet spectral range, presents a hipsochromic spectral shift as function of the electronic nature of the heteroatomic centers in the heterocyclic ring. In order to determine a spectroscopic assignment of the main absorption bands in aqueous solution and analyze the effect of the substituent on the electronic charge distributions in the ground and the first two singlet excited electronic states, we have used a semiempirical molecular orbital calculation in the INDO/S-CIS approach. On the other hand, we have carried out a molecular orbital calculation in the AM1 framework, in order to determine the energetic stability of the thiones with respect to the thiol compounds.