Intramolecular Cooperative Effects in Multichromophoric Cavitands Exhibiting Nonlinear Optical Properties

Csók, Zsolt and Szuroczki, Péter and Kollár, László and Ngo, Hoang Minh and Ledoux-Rak, Isabelle and Caturello, Naidel A. M. S. and Albuquerque, Rodrigo Q. (2015) Intramolecular Cooperative Effects in Multichromophoric Cavitands Exhibiting Nonlinear Optical Properties. The Journal of Physical Chemistry. pp. 12608-12615. ISSN 0022-3654

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Abstract

We report on the design, synthesis, and characterization of a new class of multichromophoric cavitands based on resorcin[4]arenes. The novel compounds have exhibited high values of second-order nonlinear optical (NLO) properties, as evidenced by electric-field-induced second harmonic generation (EFISHG) measurements. Theoretical calculations indicate the presence of edge-to-face T-shaped interactions between the aromatic building blocks within these multichromophoric systems, which is further supported by the detection of hypsochromic shifts in UV−vis and upfield aromatic chemical shifts in 1 H NMR. We proved for thefirst time that the gain in the quadratic hyperpolarizabilities of multichromophoric NLO macrocycles, originating from the near parallel orientations of the subchromophores, can be partially suppressed if the distance between the dipolar subunits falls into a specific range, where intramolecular cooperative and/or collective effects are operative. Ourfinding will contribute to the better understanding of the phenomenon of cooperativity in new molecular materials with promising NLO properties

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