Synthesis, characterization, and electrical conductivity of polyesterification products with tetrathiafulvalene units, and their TCNQ complexes

Abstract

Polyesterification products with tetrathiafulvalene units 3ae were prepared from tetrathiafulvalenedicarbonyl dichloride (1) and various a,w-diols (2a-e) containing 2 to 16 methylene groups. The red to brown products 3a-e with melting points between 235 "C and 128°C are insoluble in all common organic solvents, except for 3e which is soluble in hot DMF. Molecular weights determined by vapor pressure osmometry as well as from elemental analyses data have been found to be g2000. The structures were proved by IR, MS, and electronic spectra. The electrical conductivities of 3a-e are between 4.10-8 and 4.10-13 O-'-cm-'. In TCNQ complexes the electrical conductivities are enhanced by one to five orders of magnitude.

Functional polymers based on electron-donating TTF and derivatives

“…61 Pitmann Jr. and coworkers reported homo-and co-polymerization of p-(2-tetrathiafulvalenyl)phenyl methacrylate (10). 62 Unfortunately, the obtained polymers (7,9,11) resulted in poorly characterizable materials due to the problem of solubility (Scheme 2). To improve the solubility of the polymers, Mu ¨llen and coworkers attached long alkyl and alkoxy chains to the polymer backbone.…”

“…Since a first polymer containing a TTF moiety was prepared via a polycoupling process, 76 a number of attempts to incorporate such donor molecules into a polymeric framework (27) have been carried out. [5][6][7][8] Although some of them showed semiconducting properties upon doping, they were generally disordered or poorly characterizable materials. Progress in synthetic chemistry of tetrathiafulvalene derivatives during the past decade has allowed the preparation of new conjugated polymeric donor systems, in particular, the donor units incorporated in conjugated main chain systems.…”

Polymerization Mechanism of Di(benzylidene)tetrathiapentalenes into Linearly Extended TTF Polymers

“…Owing to the exciting solid-state properties of their radical cation salts, such as high electrical conductivity or even superconductivity, TTF and its derivatives have been the focus of general interest for more than 2 decades. , The potential technological applications of these materials have spurred numerous attempts to incorporate TTF radical salts into polymeric backbones to combine their electrical conductivity with the enhanced processability of macromolecular structures. To date, the polymeric TTF derivatives described in the literature have been prepared from functionalized TTF monomers and consist of essentially independent TTF moieties attached to a polymeric backbone or of segregated TTF units linked through suitable spacer groups …”