Tetrathiafulvalene in a Perylene-3,4:9,10-bis(dicarboximide)-Based Dyad: A New Reversible Fluorescence-Redox Dependent Molecular System

Abstract
A donor−acceptor dyad system involving tetrathiafulvalene (TTF) as donor attached by a flexible spacer to perylene-3,4:9,10-bis(dicarboximide) (PDI) as acceptor was synthesized and characterized. The strategy used the preliminary synthesis of an unsymmetrical PDI unit bearing an alcohol functionality as anchor group. Single-crystal analysis revealed a highly organized arrangement in which all PDI molecules are packed in a noncentrosymmetrical pattern. It was shown that the fluorescence emission intensity of the TTF−PDI dyad can be reversibly tuned depending on the oxidation states of the TTF unit. This behavior is attributed to peculiar properties of TTF linked to a PDI acceptor, which fluoresces intrinsically. Consequently, this dyad can be considered as a new reversible fluorescence-redox dependent molecular system.