Breaking of symmetrical charge distribution in xanthylocyanine chromophores detecting by their absorption spectra

• Published in: Journal of molecular structure Vol. 990; no. 1; pp. 6 - 13
• Main Authors: Vasyluk, S.V., Viniychuk, O.O., Poronik, Ye.M., Kovtun, Yu.P., Shandura, M.P., Yashchuk, V.M., Kachkovsky, O.D.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 29-03-2011
• Subjects: absorption; Absorption spectra; Cyanine dyes; dyes; electrons; Quantum-chemical calculation; Solitonic charge wave; spectral analysis; Symmetrical and unsymmetrical forms; Symmetry breaking; wavelengths; Cyanine dyes; Solitonic charge wave; Absorption spectra; Quantum-chemical calculation; Symmetrical and unsymmetrical forms; Symmetry breaking
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2010.12.047

A detailed experimental investigation and quantum-chemical analysis of symmetrical cyanines with xanthylium and its substituted derivatives and with different polymethine chain (containing 1 and 2 vinylene groups) have been performed with the goal of understanding the nature of the electronic transitions in molecules. It is established electronic transitions in carbocyanines are similar to that in the typical Brooker’s cyanines. In contrast, the absorption spectra of dicarbocyanines demonstrate a strong solvent dependence and substantial band broadening represented by the growth of the short wavelength shoulder. Basing on the results of the quantum-chemical calculation and conception of the mobile solitonic-like charge waves, we have concluded that the dicarbocyanines exist in two charged forms in the ground state with symmetrical and unsymmetrical distributions of the charge density. These are the examples of the cationic cyanines with the shortest chain when the symmetry breaking occurs.