Symmetry switching of the fluorescent excited state in alpha,omega-diphenylpolyynes.
By using MO calculations based on DFT, absorption, and fluorescence spectroscopy, we have comprehensively studied the low-lying excited singlet states of alpha,omega-diphenylpolyynes (DPY) having 1-6 triple bonds. The a(g) vibrational modes of the C(triple bond)C stretching and of the phenyl ring motion were observed in the fluorescence spectra of diphenylacetylene and 1,4-diphenylbutadiyne. On the other hand, in the fluorescence spectra of the long DPY with the triple-bond number (N) more than two, the phenyl ring motion with a(g) symmetry disappeared and the b(1g) modes of the phenyl ring twisting (approximately 400 cm(-1)) and of the C-H bending (approximately 900 cm(-1)) were detected. The observed fluorescent states of DPY with N < or = 2 and N > or = 3 are assigned to the 1(1)B(1u) (pi(x)pi(x*)) and 1(1)A(u) (pi(x)pi(y*) and/or pi(y)pi(x*)) states, respectively, based on the vibronic structures, the relatively short lifetimes, and the solvatochromic shifts of the fluorescence spectra. Not only the allowed transition of 1(1)B(1u) <-- S(0) but also the forbidden transition of 1(1)A(u) <-- S(0) was detected in the fluorescence excitation spectra of the long DPY with N > or = 3. The low-lying excited state with A(u) symmetry is characteristic in polyyne, which does not exist in polyene. The oscillator strength (f) of the first absorption band in DPY decreases with an increase in N, which is the opposite behavior of the all-trans-alpha,omega-diphenylpolyenes. The N-dependence of the f value is understood by the configuration interaction between the 1(1)B(1u) and 2(1)B(1u) (pi(y)pi(y*)) states, which is consistent with the reduction of the nonlinear optical response of polyyne.
Nagano
Yasutomo
Y
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan.
Ikoma
Tadaaki
T
Akiyama
Kimio
K
Tero-Kubota
Shozo
S