How the Central Torsion Angle Affects the Rates of Nonradiative Decay in Some Geometrically Restricted p-Quaterphenyls

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 111; no. 14; pp. 2641 - 2649
• Main Authors: Allen, Ben D., Benniston, Andrew C., Harriman, Anthony, Llarena, Irantzu, Sams, Craig A.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 12.04.2007
• Subjects: Biphenyl Compounds - chemical synthesis; Biphenyl Compounds - chemistry; Magnetic Resonance Spectroscopy - methods; Magnetic Resonance Spectroscopy - standards; Models, Chemical; Models, Molecular; Molecular Structure; Quantum Theory; Reference Standards
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp0669660

A small series of p-quaterphenyl derivatives has been prepared in which the dihedral angle (φ) for the two central rings is constrained by dialkoxy spacers of varying length. The photophysical properties of these compounds remain comparable, but there is a clear correlation between the rate constants for nonradiative decay of both singlet and triplet excited states and φ in fluid solution. The rates tend toward a minimum as φ approaches 90°. These effects are attributed to the general phenomenon of extended delocalization and can be traced to a combination of changes in the Huang−Rhys factor and the electron−vibrational coupling matrix element, both relating to displacement of the relevant potential energy surfaces and to the medium-frequency vibronic mode coupled to decay. The latter effect arises because of different levels of conjugation in the ground-state molecule. Such findings might have important implications for the design of improved light-emitting diodes. A similar angle dependence is noted for the yield of the π-radical cation formed on photoionization in a polar solvent, but here, the effect is due to variations in the respective energy gaps between the relevant excited states.