Electronic and vibrational structure in the S and S1 states of corannulene

Abstract

Corannulene is a nonplanar aromatic hydrocarbon also known as a buckybowl. Its electronic and vibrational structure has been investigated by analyzing its fluorescence excitation spectrum and dispersed fluorescence spectrum in a supersonic jet. Its spectral features are in keeping with the expectation, confirmed by some previous results, that it has fivefold or C5v symmetry. The observed prominent vibronic bands in the S1 ← S0 transition have been assigned to e1 and e2 bands on the basis of theoretical calculations so that the S1 state was assigned to 1E2. The symmetry adapted cluster configuration interaction calculation supports this assignment of the S1 electronic state, although the time-dependent density functional theory calculation suggests that the S1 state is 1A2. It has also been shown that the normal coordinates for strong vibronic bands mainly include out-of-plane vibrational motion. The rotational envelopes are well explained by taking account of the Coriolis interaction between the degenerate vibrational and rotational levels. The mechanism of bowl-to-bowl inversion is also discussed with the results of theoretical calculations regarding the barrier to inversion and metastable conformation.

Curved Nanographenes: Multiple Emission, Thermally Activated Delayed Fluorescence, and Non‐Radiative Decay

“…Simultaneously k nr + k ISC = k − k r = 𝜏 −1 − k r = 1.01 × 10 8 s −1 is obtained from those values. In fact, for Cor the S 0 ←S 1 transition is electric-dipole forbidden and its electronic origin can be expected at ≈380 nm, [28] consistent with our observations. A similar situation exists for non-functionalized HBC, [29] where a forbidden electronic origin at 428 nm was reported, again in agreement with the calculations and with spectra shown in Figure S7 (Supporting Information).…”