title: Syntheses and unusual segregated-alternated hybrid stacking structure of hydrogen-bonded charge-transfer complexes composed of bis[2,3-pyridinedithiolate]metal complexes.
abstract: We report the syntheses of new planar electron donor inorganic molecules [bis(2,3-pyridinedithiolate)metal(II)]; [MII(Hpydt)2] (M = Ni(1), Pd(2), Pt(3)) and their anions; [MII(pydt)2]2- (M = Ni(4), Pd(5)), which are equipped with both a highly lying highest occupied molecular orbital (HOMO) perpendicular to the plane and hydrogen-bonding capability in the plane. In addition, we present two novel hydrogen-bonded charge-transfer (HBCT) complexes, [M(Hpydt)2]TCNQ (M = Ni, Pd), with 7,7,8,8-tetracyanoquinodimethane (TCNQ). All the neutral and ionic inorganic molecules and the HBCT complexes were successfully characterized by single-crystal X-ray crystallography. The HBCT complexes show an unusual segregated-alternated hybrid stacking structure in which each component interacts parallel to the stacks with neighboring donors and acceptors. Furthermore, the structural network is expanded as a result of a one-dimensional hydrogen-bonding chain formed between donors and acceptors perpendicular to the stacking direction. The theoretical electronic structures of the HBCT complexes are also reported.
authors.affiliation: Department of Chemistry, Faculty of Science, Kyushu University, Hakozaki 6-10-1, Higashi-ku, Fukuoka 812-8581, Japan. sota-s.scc@mbox.nc.kyushu-u.ac.jp
authors.forename: Sota
authors.initials: S
authors.lastname: Shibahara
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Kitagawa
authors.forename: Yoshiki
authors.initials: Y
authors.lastname: Ozawa
authors.forename: Koshiro
authors.initials: K
authors.lastname: Toriumi
authors.forename: Takashi
authors.initials: T
authors.lastname: Kubo
authors.forename: Kazuhiro
authors.initials: K
authors.lastname: Nakasuji