Optical spectra of two families of symmetrical polymethine dyes, bearing a positive and a negative charge, are analyzed based on an essential-state model recently developed for quadrupolar dyes. The model accounts for molecular vibrations and polar solvation and reproduces the anomalous evolution with solvent polarity of experimental absorption band shapes. Fluorescence and excited-state absorption spectra are well-described within the same model, which also quantitatively reproduces the recent observation of an intense two-photon absorption toward the (two-photon forbidden) lowest excited state. An extensive analysis of optical spectra demonstrates that the essential-state model developed for quadrupolar dyes also applies to polymethine dyes and that long polymethine dyes offer the first experimental example of class III quadrupolar chromophores.

Essential-State Model For Polymethine Dyes: Symmetry Breaking And Optical Spectra / Terenziani, Francesca; O. V., Przhonska; S., Webster; L. A., Padilha; Y. L., Slominsky; I. G., Davydenko; A. O., Gerasov; Y. P., Kovtun; M. P., Shandura; A. D., Kachkovski; D. J., Hagan; E. W., Van Stryland; Painelli, Anna. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 1:12(2010), pp. 1800-1804. [10.1021/jz100430x]

Essential-State Model For Polymethine Dyes: Symmetry Breaking And Optical Spectra

TERENZIANI, Francesca;PAINELLI, Anna
2010-01-01

Abstract

Optical spectra of two families of symmetrical polymethine dyes, bearing a positive and a negative charge, are analyzed based on an essential-state model recently developed for quadrupolar dyes. The model accounts for molecular vibrations and polar solvation and reproduces the anomalous evolution with solvent polarity of experimental absorption band shapes. Fluorescence and excited-state absorption spectra are well-described within the same model, which also quantitatively reproduces the recent observation of an intense two-photon absorption toward the (two-photon forbidden) lowest excited state. An extensive analysis of optical spectra demonstrates that the essential-state model developed for quadrupolar dyes also applies to polymethine dyes and that long polymethine dyes offer the first experimental example of class III quadrupolar chromophores.
2010
Essential-State Model For Polymethine Dyes: Symmetry Breaking And Optical Spectra / Terenziani, Francesca; O. V., Przhonska; S., Webster; L. A., Padilha; Y. L., Slominsky; I. G., Davydenko; A. O., Gerasov; Y. P., Kovtun; M. P., Shandura; A. D., Kachkovski; D. J., Hagan; E. W., Van Stryland; Painelli, Anna. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 1:12(2010), pp. 1800-1804. [10.1021/jz100430x]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2310128
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