title: Experimental and theoretical study on the one- and two-photon absorption properties of novel organic molecules based on phenylacetylene and azoaromatic moieties.
abstract: This Article reports a combined experimental and theoretical analysis on the one and two-photon absorption properties of a novel class of organic molecules with a π-conjugated backbone based on phenylacetylene (JCM874, FD43, and FD48) and azoaromatic (YB3p25) moieties. Linear optical properties show that the phenylacetylene-based compounds exhibit strong molar absorptivity in the UV and high fluorescence quantum yield with lifetimes of approximately 2.0 ns, while the azoaromatic-compound has a strong absorption in the visible region with very low fluorescence quantum yield. The two-photon absorption was investigated employing nonlinear optical techniques and quantum chemical calculations based on the response functions formalism within the density functional theory framework. The experimental data revealed well-defined 2PA spectra with reasonable cross-section values in the visible and IR. Along the nonlinear spectra we observed two 2PA allowed bands, as well as the resonance enhancement effect due to the presence of one intermediate one-photon allowed state. Quantum chemical calculations revealed that the 2PA allowed bands correspond to transitions to states that are also one-photon allowed, indicating the relaxation of the electric-dipole selection rules. Moreover, using the theoretical results, we were able to interpret the experimental trends of the 2PA spectra. Finally, using a few-energy-level diagram, within the sum-over-essential states approach, we observed strong qualitative and quantitative correlation between experimental and theoretical results.
authors.affiliation: Instituto de Física de São Carlos, Universidade de São Paulo, Caixa Postal 369, 13560-970 São Carlos, SP, Brazil. mavivas82@yahoo.com.br
authors.forename: Marcelo G
authors.initials: MG
authors.lastname: Vivas
authors.forename: Daniel L
authors.initials: DL
authors.lastname: Silva
authors.forename: Leonardo
authors.initials: L
authors.lastname: De Boni
authors.forename: Yann
authors.initials: Y
authors.lastname: Bretonniere
authors.forename: Chantal
authors.initials: C
authors.lastname: Andraud
authors.forename: Florence
authors.initials: F
authors.lastname: Laibe-Darbour
authors.forename: J-C
authors.initials: JC
authors.lastname: Mulatier
authors.forename: Robert
authors.initials: R
authors.lastname: Zaleśny
authors.forename: Wojciech
authors.initials: W
authors.lastname: Bartkowiak
authors.forename: Sylvio
authors.initials: S
authors.lastname: Canuto
authors.forename: Cleber R
authors.initials: CR
authors.lastname: Mendonca