ja994497s_si_001.pdf (470.47 kB)
Structure−Property Relationships for Two-Photon Absorbing Chromophores: Bis-Donor Diphenylpolyene and Bis(styryl)benzene Derivatives
journal contribution
posted on 2000-09-13, 00:00 authored by Mariacristina Rumi, Jeffrey E. Ehrlich, Ahmed A. Heikal, Joseph W. Perry, Stephen Barlow, Zhongying Hu, Dianne McCord-Maughon, Timothy C. Parker, Harald Röckel, Sankaran Thayumanavan, Seth R. Marder, David Beljonne, Jean-Luc BrédasThe two-photon absorption properties of a series of bis dialkylamino- or diarylamino-substituted
diphenylpolyenes and bis(styryl)benzenes have been investigated. Two-photon absorption cross sections, δ, as
large as 1420 × 10-50 cm4 s/photon-molecule have been observed for molecules with this general bis-donor
structure. The effect of the type and length of the conjugated chain and of dialkylamino or diarylamino
substitution on the position and magnitude of the peak two-photon absorptivity is reported. The transition
dipole moments for the transitions between the ground state and the first excited singlet state (Mge) and between
the first and second excited singlet states (Mee‘) have been estimated using experimental data from the one-
and two-photon spectra. It was found that increases in chain length result mainly in an increase in Mge, whereas
the addition of donor end groups or going from diphenylpolyene- to phenylene-vinylene-type bridges leads
primarily to an increase in Mee‘. The trends in the energy of the lowest excited singlet states and in the transition
moments for the diphenylpolyene series as a function of chain length are in agreement with those calculated
by quantum mechanical methods. These results furnish a link between structural features in these classes of
molecules and the electronic dipole couplings and state energies that control the strength of the two-photon
absorption. In bis(aminophenyl)polyenes containing up to four double bonds (m) the lowest excited singlet
state is a Bu state, as opposed to the case of simple polyenes and diphenylpolyenes, for which it is an Ag state
for m > 2. The relationship of the state ordering in these systems with the observed values of the radiative and
nonradiative decay rates is also discussed.