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

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.

本研究合成并表征了一种给体-受体二元体系：以四硫富瓦烯（tetrathiafulvalene, TTF）作为给体，通过柔性间隔基与作为受体的苝-3,4:9,10-双二酰亚胺（perylene-3,4:9,10-bis(dicarboximide), PDI）相连。该合成策略首先制备了带有醇羟基作为锚定基团的不对称PDI单元。单晶分析结果显示，该体系呈现高度有序的排列结构，所有PDI分子均以非中心对称的方式堆积。研究表明，TTF-PDI二元体系的荧光发射强度可根据TTF单元的氧化态进行可逆调控。该行为归因于与PDI受体相连的TTF所具有的独特性质，而PDI受体本身具有固有荧光特性。因此，该二元体系可被视为一种新型的、依赖于荧光-氧化还原响应的可逆分子体系。