Excited states of [3.3](4,4')biphenylophane: the role of charge-transfer excitations in dimers with pi-pi interaction.
The singlet and triplet electronic excitation manifold of [3.3](4,4')biphenylophane (BPP), an intramolecular dimer, and 4,4'-dimethylbiphenyl (DMBP), the corresponding monomer, has been analyzed by employing the approximate coupled-cluster singles and doubles model (CC2). The calculated triplet-triplet and singlet-singlet transient absorption spectra show good agreement with recent experimental results. The calculations suggest a strong interaction of the two biphenyl moieties of BPP in the first singlet and triplet excited states due to the overlapping pi-electron systems, and Forster-Dexter theory for weak coupling cannot be applied. Both the first excited singlet and triplet states of BPP can be characterized as excimeric states with a strong admixture of charge-transfer contributions.
Pabst
Mathias
M
Institut für Physikalische Chemie, Johannes Gutenberg-Universität Mainz, Jakob Welder-Weg 11, 55099 Mainz, Germany. pabst@uni-mainz.de
Köhn
Andreas
A