Structural investigation of model compounds for an acceptor component of a new type of charge-transfer complexes based on viologen analogues. Characteristic features of the molecular and supramolecular structures

Abstract

The crystal and molecular structures of six perchlorates (viologen analogues) are studied. These compounds serve as models of the acceptor component of new charge-transfer complexes containing bis(18-crown-6)stilbene as the donor. The polycyclic aromatic system of divalent cations is demonstrated to be virtually planar. In all cations, the side chains at the nitrogen atoms are oriented in opposite directions almost perpendicular to the plane of the cyclic system. This orientation of the spacers of these carbocations is indicative of their preorganization for the formation of 1: 2 charge-transfer complexes. Analysis of the crystal packings provides evidence that two positive charges on the conjugated systems of the organic cations and the perchlorate anions play a destructive role in the formation of stacking motifs. An increase in the size of the conjugated system and the involvement of an aromatic solvent molecule as an additional building block in a supramolecular system are favorable for the formation of a stacking supramolecular architecture.