Effect of Solute−Solvent Compatibility on Total Luminescence Spectra of Perylene in Shpol'skii Matrixes at Liquid Helium Temperature

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 106; no. 18; pp. 4552 - 4557
• Main Authors: Palewska, Krystyna, Lipiński, Józef, Misiaszek, Tomasz, Sworakowski, Juliusz
• Format: Journal Article
• Language: English
• Published: American Chemical Society 09.05.2002
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp020493p

Fluorescence excitation and emission spectra of perylene in n-alkane Shpol'skii matrixes have been studied at liquid helium temperature. The presence of a dominant Shpol'skii site has been detected in all matrixes and attributed to perylene molecules substitutionally entering the host lattice. The character of the highest-energy site observed in all matrixes was found to be strongly dependent on the nature of solvent. Three matrixes were selected for a comparative study:  n-hexane, forming a “good” matrix, and n-decane and n-undecane, forming “poor” matrixes. A vibrational analysis of all Shpol'skii sites was performed, and an additional low-frequency out-of-plane vibration at ca. 190 cm-1 was observed for the highest energy site in n-decane and n-undecane matrixes in highly resolved two-dimensional spectra. Vibrational frequencies detected in “conventional” emission and excitation spectra and in two-dimensional spectra, as well as data from infrared and Raman spectra, are in a good agreement with recalculated vibrational frequencies obtained by MNDO and ab initio quantum-chemical methods.