Molecular structures of (a) rylenes and (b) heteroatom X-annulated quaterrylene: X 1 = X 2 = N, N, N, N-annulated quaterrylene (QNN); X 1 = S, X 2 = N, N, S-annulated quaterrylene (QNS); X 1 = X 3 = N, NQN; X 1 = N, X 3 = S, NQS.
The atomic orbital composition of selected molecular orbitals in perylene, terrylene, and quaterrylene at the B3LYP/6–31G*level.
B3LYP/6–31g* HOMO (left) and LUMO (right) orbitals.
The low-lying excited states of quaterrylene and the X-annulated quaterrylene calculated by using the MRCI/ZINDO. The transition oscillator strengths are given in parenthesis, and the point groups are shown for the molecules at the ground state at the bottom.
(a) The absorption spectra at T = 20 K of perylene (solid for the calculated spectrum and dash dot for the experimental one); (b) the emission spectra of perylene (solid line for the T = 20 K, dash dot for T = 300 K) and their assignments of transition (vertical lines) which are labeled as N ν (N is the index of the excited normal modes and ν is the quantum number).
The dominant normal modes involved in the emission spectra for perylene. The corresponding frequencies of normal modes are shown in parentheses.
Theoretical emission spectra for the X-annulated quaterrylene derivatives at T = 300 K.
Theoretical emission spectra for tri-N-annulated hexarylene (HNNN) and tetra-N-annulated octerylene.
Vertical excitation energies (eV) of the four low-lying excited states at the ground state geometry for the oligorylenes. The oscillator strengths of the dipole-allowed states are given in the parenthesis.
The main configurations in CASSCF wave function of the two low-lying states of oligorylenes. The orbital symmetry, and the selected weight (>0.10) in the wave function are given.
The frequencies of active modes involved in the emission process for the X-annulated quaterrylene derivatives.
The calculated radiative and nonradiative transition rates from S1 to S0 rates for the oligorylenes and the X-annulated rylene derivatives.
Article metrics loading...
Full text loading...