Organic Nanoclusters for Nonlinear Optics: from Model Systems to Cooperative Nanoassemblies with Enhanced NLO Responses

While structure-properties relationships are quite actively and successfully investigated at the molecular level of engineering of optical nonlinear responses, supramolecular structure-property relationships are an appealing field. The realization that interchromophoric interactions between strongly polar/polarizable NLO chromophores can significantly affect the NLO response of each chromophoric unit as well as promote associations has opened new dimensions for molecular design. Several elegant routes have been implemented to hinder or counterbalance dipole-dipole interactions between dipolar NLO chromophores for the elaboration of second-order materials (for SHG or electro-optical modulation). At opposite, we have implemented a reverse strategy by confining discrete numbers of NLO push-pull chromophores in close proximity within covalent organic nanoclusters with the aim to exploit interchromophoric interactions in order to achieve enhanced NLO responses. As a proof of concept, we present here the investigation of two-series of multichromophoric covalent assemblies built from NLO push-pull chromophores showing that cooperative enhancement can be achieved both for second-order optical responses (first hyperpolarizabilities) or third-order responses (two-photon absorption cross-sections).