Authors:
M. Hayashi, K. Otsubo, M. Maesato, T. Komatsu, K. Sugimoto, A. Fujiwara, H. Kitagawa

Abstract:
An electrically conductive D−A−D aggregate composed of a single component was first constructed by use of a protonated bimetal dithiolate (complex 1H2). The crystal structure of complex 1H2 has one-dimensional (1-D) π-stacking columns where the D and A moieties are placed in a segregated-stacking manner. In addition, these segregated-stacking 1-D columns are stabilized by hydrogen bonds. The result of a theoretical band calculation suggests that a conduction pathway forms along these 1-D columns. The transport property of complex 1H2 is semiconducting (Ea = 0.29 eV, ρrt = 9.1 × 104 Ω cm) at ambient pressure; however, the resistivity becomes much lower upon applying high pressure up to 8.8 GPa (Ea = 0.13 eV, ρrt = 6.2 × 10 Ω cm at 8.8 GPa). The pressure dependence of structural and optical changes indicates that the enhancement of conductivity is attributed to
not only an increase of π−π overlapping but also a unique pressure-induced intramolecular charge transfer from D to A moieties in this D−A−D aggregate.

Link:
Inorg. Chem. 55 (2016) 13027–13034.
DOI: 10.1021/acs.inorgchem.6b02301