Electronic spectra of jet-cooled 1,4-bis(phenylethynyl)benzene: Strength in π-electron conjugation and two large-amplitude torsional motions.

Abstract

To spectroscopically qualify strength in the π-electron conjugation, the electronic spectra of jet-cooled 1,4-bis(phenylethynyl)benzene (BPEB) in the region of the transition to the lowest excited singlet (S1) 1B1u state are measured by the fluorescence excitation and the single-vibronic-level dispersed fluorescence methods. Strength is defined as the difference in potential energies between the planar and perpendicular conformations. BPEB possesses two large-amplitude torsional motions, out-of-phase 24 and in-phase 29 modes. The most stable is the planar conformation, and barrier heights at the perpendicular conformation are coincident in torsional potentials for the two modes. Torsional levels are successively observed up to 19± and 16- quantum levels in the ground state, respectively. Strength is determined to be 293cm-1 (3.51 kJmol-1) with an accuracy of an error range smaller than 1cm-1. In the excited state, strength is estimated to be 1549 ± 73cm-1. Combination levels of two torsional modes are also measured up to high quantum levels. A systematic decrease in frequencies is observed with increasing the quantum number. Quantum-chemistry calculations of B3LYP, CAM-B3PLYP, WB97XD, and M062X with basis sets of aug-cc-pVDZ are performed, where B3LYP theories are carried out with the dispersion correlation. The calculated strength is 1.1-2.1 times larger than observed.