Abstract
Unlike the previous several investigations on planar donor-π-acceptor chromophores, the present investigation highlights the importance of twisted molecular configurations to effectively tune the optical and nonlinear optical (NLO) response properties. A variety of substitutions are made to design several twisted molecular compounds (1–7). These compounds are designed using pyrenyl and naphthalimide moieties, which are twisted with each other in their molecular configurations. The calculated versus experimental highest intensity absorption energy peaks (3.482 V. 3.444 eV) and experimental ionization potentials (6.07 V. 5.93 eV) of parent compound 1 reproduced reasonably well at M06/6-311G∗∗ methodology. The twisted chromophores show significantly larger amplitudes of third-order NLO polarizabilities (<γ>), which are found to be as large as 778.31 × 10−36 esu for compound 7 at the M06/6-311G∗∗ methodology. The <γ> amplitudes were also compared with planar donor-π-acceptor prototype para-nitroaniline (p-NA) molecule to provide the semi-quantitative assessment. For instance, the <γ> amplitudes of all compounds are about ∼7–∼39 times bigger from the amplitude of p-NA at the same computational level. The origin of larger amplitudes has been traced though three-level model using the TD-DFT results. The larger oscillator strengths, lower transitions energies and larger change between the electronic dipole moment between the ground and the excited states. We believe the present study will not only put these compounds under the spotlight of material science but also provide structure-property relationships in designed compounds.
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•The twisted molecular configurations are explored for NLO.•Origin of larger NLO amplitudes traced is in better ICT process.•The hyperpolarizability density (ρzzz(3)(r)) analysis is performed.•Effects of donor and acceptor substitutions have been studied.•The FMO and MEPs are drawn to see charge distributions.