Formation of charge-transfer complexes in ionic crystals composed of 1,3-bis(dicyanomethylidene)indan anion and viologens bearing alkyl chains

Abstract

The relationship between charge-transfer (CT) properties and the molecular arrangement formed from π-electronic ion pairs remains unclear because of the limited variety of π-electron anions. This study addressed this issue by synthesising a series of ion pair assemblies composed of viologen dications with diverse alkyl chains as π-electron cations and 1,3-bis(dicyanomethilidene)indan anion (CMI⁻) as a stable π-electron anion. We obtained seven ionic crystals and identified their assembled structures using single-crystal X-ray analysis. These structures are categorized into three types: “columnar”, “slipped columnar” and “independent”. The CT properties were characterised using UV-Vis absorption spectroscopy, which revealed that the CT absorption bands were dependent on the alkyl chain length. This intriguing variation in the CT transitions can be explained by the differences in the type of assembled structure.