Preparation and physical properties of nanoaggregates composed of charge-transfer complexes containing butadiyne derivatives with tetrathiafulvalene moieties

Abstract

Nanoaggregates of three butadiyne derivatives, i.e., butadiyne derivatives with one tetrathiafulvalene (TTF) moiety at one end (BUT1), two TTF moieties at both ends (BUT2), and one TTF moiety directly bound to the butadiyne group (TBU), and their charge-transfer (CT) complexes with 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane (F2TCNQ) were prepared by the reprecipitation method. The nanoaggregate sizes of BUT1, BUT2, and TBU were about 80–200 nm and those of the CT complexes were reduced to about 100 nm. Upon UV irradiation, nanoaggregates of BUT1 showed regular 1,4-addition polymerization in the solid state while those of BUT2 and TBU polymerized in an irregular manner. However, solid-state polymerization of their CT complexes was not confirmed and decomposition of the complexes was observed. From the X-ray study, the crystallinity of the nanoaggregates was found to degrade in general, compared with that of the corresponding bulk crystals. Interestingly, nanoaggregates of BUT1-F2TCNQ and BUT2-F2TCNQ complexes were found to have conductivities of more than 10−6 S/cm, although their bulk crystals did not show measurable conductivities.