Details

Autor(en) / Beteiligte

• Sonoda, Yoriko
• Goto, Midori
• Tsuzuki, Seiji
• Tamaoki, Nobuyuki

Titel

Fluorinated Diphenylpolyenes:  Crystal Structures and Emission Properties

Ist Teil von

• The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2007-12, Vol.111 (51), p.13441-13451

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2007

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• (E,E,E)-1,6-Diaryl(Ar)-1,3,5-hexatrienes (2, Ar = 4-fluorophenyl; 3, Ar = 2,4-difluorophenyl; 4, Ar = 2,4,6-trifluorophenyl; 5, Ar = perfluorophenyl) and (E,E,E)-1-perfluorophenyl-6-phenyl-1,3,5-hexatriene (6) were prepared. The absorption and fluorescence spectra in methylcyclohexane solution showed only a small dependence on the fluorine ring substituent, and were similar to those of the unsubstituted parent compound (1, Ar = phenyl). The solid-state absorption and fluorescence spectra shifted to red relative to those in solution and strongly depended on the substituent. The emission from crystals 1 − 5 originated mainly from monomeric species with the maximum wavelength (λf(max)) of 440−465 nm, which overlapped the emission from molecular aggregates (1 − 4) or excimeric species (5) in the red region. Crystal 6 exhibited red-shifted (λf(max) = 530 nm) and structureless emission due to excimers. The cocrystal of 1 and 5 (1/5) showed red-shifted (λf(max) = 558 nm) and distinctly structured emission, not from exciplexes but from the excited states of molecular aggregates in which molecules 1 and 5 strongly interact already in the ground state. These assignments were confirmed by the results of fluorescence lifetime and quantum yield measurements in the solid state. Single-crystal X-ray structure analyses showed that the molecules were basically planar in each crystal, whereas the crystal packing was strongly substituent-dependent. Weak π−π interactions in the herringbone (1 and 2) and in the π-stacked but largely offset structures (3 and 4) account for their predominantly monomeric origin of emission. The observation of excimer fluorescence from 5 was rather unexpected, since the molecules in this crystal were arranged in an offset stacking fashion due to perfluorophenyl−perfluorophenyl (C6F5···C6F5) interaction. The structures of 6 and 1/5 considerably resembled each other, in which molecules were π-stacked with more face-to-face geometries than those in 5, as a result of strongly attractive perfluorophenyl−phenyl (C6F5···C6H5) interaction. Nevertheless, the fluorescence origin was clearly different for 6 and 1/5. This can be ascribed to the difference in the strength of orbital−orbital interaction between molecular π-planes in the ground and excited states in crystals.