Influence of π-stacking on the resonant enhancement of the second-order nonlinear optical response of dipolar chromophores

Wei Zhang, Anthony F. Cozzolino, Amir H. Mahmoudkhani, Mark Tulumello, Sarah Mansour, Ignacio Vargas-Baca

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

The wavelength-dependent second-harmonic generation (SHG) efficiency of two simple dipolar chromophores, 4-NO2C6H4N(H) Bun (1) and 4-NO2C6H4SN(H)Bu t (2), was compared in solution and in the solid state. Hyper-Rayleigh scattering measurements at 532 nm provided comparable molecular first hyperpolarizabilities. Both compounds crystallize in non-centrosymmetric space groups, but a more efficient arrangement of dipole moments results in a significantly larger deff value for 2. Kurtz-Perry experiments from 450 to 700 nm revealed an important difference in the resonant component of the nonlinear optical responses of these compounds; the SHG efficiency of crystalline 1 depends more strongly on the incident wavelength than that of 2. This would be in contradiction with the TD-DFT excitation energies calculated for these molecules, but the observation can be explained by the resonant contribution from low-energy interchromophore excitations enabled by π-stacking in the crystal of 1.

Original languageEnglish
Pages (from-to)18378-18384
Number of pages7
JournalJournal of Physical Chemistry B
Volume109
Issue number39
DOIs
StatePublished - Oct 6 2005

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