Cooperative TPA enhancement via through-space interactions in organic nanodots built from dipolar chromophores

Whereas structure-properties relationships have been widely investigated at the molecular level, supramolecular structure-property relationships have been somewhat overlooked. In many cases, interchromophoric interactions are found to be detrimental (in particular in second-order NLO) and a lot of efforts have been devoted to circumvent and control these effects to achieve efficient NLO materials for electrooptics. At opposite, we have implemented a countermainstream route based on the confinement of push-pull chromophores in close proximity within organic nanodots where both their number and relative position/distance are controlled by covalent attachment onto appropriate organic scaffolds. In such multichromophoric organic superstructures (namely covalent nanoclusters), dipole-dipole interactions can be tuned by playing on the internal architecture (topology, number of chromophoric subunits, length of the covalent linkers) and on the nature and properties (polarity, polarizability) of the chromophoric subunits. Following this strategy, we present the investigation of two series of such organic nanoclusters built from push-pull chromophores where through-space interactions are shown to modify both one-photon (OPA) and two-photon absorption (TPA) of each chromophoric subunits leading to cooperative enhancement of TPA properties and improved transparency.