title: Stepwise neutral-ionic phase transitions in a covalently bonded donor/acceptor chain compound.
abstract: Neutral (N)-ionic (I) transitions in organic donor (D)/acceptor (A) charge-transfer complexes are intriguing because a 'reservoir of functions' is available. For systematically controlling N-I transitions, tuning the ionization potential of D and the electron affinity of A is extremely important. However, the effect of Coulomb interactions, which likely causes a number of charge-gap states at once in a system bringing about stepwise transitions, is a long-standing mystery. Here, we show definite evidence for stepwise N-I transitions caused by contributions from anisotropic interchain Coulomb interactions in a metal-complex-based covalently bonded DA chain compound, [Ru(2)(2,3,5,6-F(4)PhCO(2))(4)(DMDCNQI)]·2(p-xylene) (1; 2,3,5,6-F(4)PhCO(2)(-) = 2,3,5,6-tetrafluorobenzoate; DMDCNQI = 2,5-dimethyl-N,N'-dicyanoquinonediimine), where the [Ru(2)(II,II)(2,3,5,6-F(4)PhCO(2))(4)] moiety has a paddlewheel diruthenium(II,II) motif with a Ru-Ru bond. An intermediate-temperature phase involving self-organized N and I chains was observed in the temperature range between 210 K (= T(2)) and 270 K (= T(1)) with N phase at T > T(1) and I phase at T < T(2). Accompanying the charge transitions, the spin-ground states as well as the ferrimagnetic ordering in the I phase vary. The stepwise feature of the N-I transition with a highly sensitive magnetic response should bring about new dynamical functionalities associated with charge, spin, and lattice.
authors.affiliation: Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Sendai 980-8578, Japan. miyasaka@se.kanazawa-u.ac.jp
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Miyasaka
authors.forename: Natsuko
authors.initials: N
authors.lastname: Motokawa
authors.forename: Tamiko
authors.initials: T
authors.lastname: Chiyo
authors.forename: Miho
authors.initials: M
authors.lastname: Takemura
authors.forename: Masahiro
authors.initials: M
authors.lastname: Yamashita
authors.forename: Hajime
authors.initials: H
authors.lastname: Sagayama
authors.forename: Taka-hisa
authors.initials: TH
authors.lastname: Arima