Journal of Physical Chemistry B, Vol.111, No.37, 10905-10914, 2007
Intramolecular singlet and triplet excimers of triply bridged [3.3.n](3,6,9)carbazolophanes
Inter-moiety electronic interactions in the singlet and triplet excimer states of triply bridged [3.3.n](3,6,9)-carbazolophanes ([3.3.n]Cz, n = 3-6) were studied by emission and transient absorption measurements. In these [3.3.n]Cz molecules, the dihedral angle and the separation distance r between fully overlapped two arbazole rings change systematically from nearly parallel (n = 3, r = 3.35 A) to oblique (n = 6, r = 4.03 angstrom). In rigid glass at 77 K, [3.3.n]Cz (n = 3, 4) (r < 4 angstrom) exhibited red-shifted and structureless excimer fluorescence and phosphorescence while [3.3.n]Cz (n = 5, 6) (r > 4 angstrom) exhibited monomer-like vibrational fluorescence and phosphorescence. In solution at 130 K, all [3.3.n]Cz molecules exhibited an excimeric fluorescence band while [3.3.5]Cz still exhibited monomer-like phosphorescence. Transient absorption spectra measured at 294 K exhibited local excitation and charge-transfer bands for all [3.3.n]Cz molecules in the excited singlet and triplet states, suggesting that not only singlet but also triplet excimers of carbazole are formed at room temperature. Furthermore, the singlet-triplet energy gap decreased with the decrease in n, suggesting that electrons are effectively delocalized over the two carbazole moieties. These findings showed that both singlet and triplet excimers of carbazole are formed with a separation distance shorter than about 4 angstrom and are most stable in the parallel-sandwich structure and that the configurational mixing between exciton resonance and charge resonance states plays an essential role in the formation of singlet and triplet excimers of carbazole.