Intramolecular Cooperative and Anti-Cooperative Effect on the Two-Photon Absorption Cross Section in Triphenylamine Derivatives

Author(s)

Fonseca, Ruben D. ^{[1, 2]} ; Vivas, Marcelo G. ^[3] ; Silva, Daniel Luiz ^[4] ; Eucat, Gwenaelle ^[5] ; Bretonniere, Yann ^[5] ; Andraud, Chantal ^[5] ; Mendonca, Cleber R. ^[1] ; De Boni, Leonardo ^[1]

Affiliation

^[1] Univ Sao Paulo, Inst Fis Sao Carlos, BR-13560970 Sao Carlos, SP - Brazil

^[2] Univ Popular Cesar, Dept Fis, Valledupar 2000004, Cesar - Colombia

^[3] Univ Fed Alfenas, Lab Espect Opt & Foton, BR-37715400 Pocos De Caldas, MG - Brazil

^[4] Univ Fed Sao Carlos, Dept Ciencias Nat Matemat & Educ, Rod Anhanguera Km 174, BR-13600970 Araras, SP - Brazil

^[5] Univ Claude Bernard Lyon 1, Univ Lyon, CNRS UMR 5182, Lab Chim, Ens Lyon, F-69342 Lyon - France

• Document type: Journal article
• Source: Journal of Physical Chemistry Letters; v. 10, n. 9, p. 2214-2219, MAY 2 2019.
• Web of Science Citations: 0

Abstract

The intramolecular cooperative effect in branched molecules is a consequence of the interaction and extent of electronic coupling among the different axes of charge transfer. Such an effect is the key to obtain remarkable nonlinear optical response in molecular systems. Here we show that triphenylamine derivative molecules containing only two branches present the strongest electronic interaction between them at the excited state, generating exponential enhancement of the 2PA cross section. The primary factor for such behavior was ascribed to the substantial extent and interaction of the pi-electron delocalization promoted by the strong electron-donating and acceptor antisymmetrical groups present in each branch. However, for the three-branch molecules we observed an anticooperative effect, i.e., the 2PA cross section decreases as compared to the one-branch structure as we normalized the signal by the effective 7 pi-electron number in each molecule. (AU)

• FAPESP's process: 16/20886-1 - Ultrafast nonlinear optical spectroscopy: Transient Absorption and optical Kerr Gate with polarization control
• Grantee: Leonardo de Boni
• Support Opportunities: Regular Research Grants
• FAPESP's process: 15/20032-0 - Study on Nonlinear and Charge Transport Properties of Multi-branched Molecules via Quantum Chemical Methods.
• Grantee: Daniel Luiz da Silva
• Support Opportunities: Regular Research Grants
• FAPESP's process: 11/12399-0 - Femtosecond pulses applied to nonlinear optics: spectroscopy, pulse shaping and microfabrication
• Grantee: Cleber Renato Mendonça
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 18/11283-7 - Nonlinear photonics: spectroscopy and advanced processing of materials
• Grantee: Cleber Renato Mendonça
• Support Opportunities: Research Projects - Thematic Grants