Synthesis of New Electron Donor ClMe3-TTP: Structures and Properties of (ClMe3-TTP)3X (X = PF6 and AsF6)

Abstract

In this study, we synthesized 2-(4-chloro-5-methyl-1,3-dithiol-2-ylidene)-5-(4,5-dimethyl-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (ClMe3-TTP). Results show that the cation radical salts of ClMe3-TTP with PF6− and AsF6− anions show high conductivities (101 S cm−1) at room temperature and semiconducting behavior with low activation energy (24–27 meV). A crystal structure analysis of the PF6− and AsF6− salts reveals a 3:1 donor–anion ratio of these salts. The ClMe3-TTP molecules form one-dimensional columns along the a axis, and tape-structures, connected by the side-by-side S···S interactions, also form along the a axis. The calculated intracolumn and intratape overlap integrals are relatively large; however, the overlap integrals between the one-dimensional columns and the tapes are approximately 1/2–1/5 the value of the intracolumn and intratape overlap integrals. The band calculations suggest that they have one-dimensional electronic structures, indicating that they would comprise a Mott insulator.

Dihedral-Angle Dependence of Intermolecular Transfer Integrals in BEDT-BDT-Based Radical-Cation Salts with θ-Type Molecular Arrangements

“…The highest occupied molecular orbitals (HOMOs) in these molecules are largely localized on the sulfur atoms in the 1,3-dithiol-2-ylidene (DY) unit. Therefore, TTF and TTP derivatives have very similar HOMO shapes [5,7].…”

“…The highest occupied molecular orbitals (HOMOs) in these molecules are largely localized on the sulfur atoms in the 1,3-dithiol-2-ylidene (DY) unit. Therefore, TTF and TTP derivatives have very similar HOMO shapes [5,7]. The molecular orbitals of organic materials are unique to each molecule; therefore, theoretically, there are nearly infinite options.…”