An Electrically Conductive Single-Component Donor-Acceptor-Donor Aggregate with Hydrogen-Bonding Lattice

作者：Hayashi Mikihiro^*; Otsubo Kazuya; Maesato Mitsuhiko; Komatsu Tokutaro; Sugimoto Kunihisa; Fujiwara Akihiko; Kitagawa Hiroshi^*

来源：Inorganic Chemistry, 2016, 55(24): 13027-13034.

DOI：10.1021/acs.inorgchem.6b02301

An electrically conductive D-A-D aggregate composed of a single component was first constructed by use of a protonated bimetal dithiolate (complex 1H(2)). The crystal structure of complex 1H(2) has one-dimensional (1-D) pi-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 1H(2) is semiconducting (E-a = 0.29 eV, rho(rt) = 9.1 X 10(4) Omega cm) at ambient pressure; however, the resistivity becomes much lower upon applying high pressure up to 8.8 GPa (E-a = 0.13 eV, rho(rt) = 6.2 X 10 Omega 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 pi-pi overlapping but also a unique pressure-induced intramolecular charge transfer from D to A moieties in this D-A-D aggregate.

• 出版日期2016-12-19