title: Charge transfer complexes of metal-free phthalocyanine radical anions with decamethylmetallocenium cations: (Cp*2Co+)(H2Pc˙-)·solvent and (Cp*2Cr+)(H2Pc˙-)·4C6H4Cl2.
abstract: Charge transfer complexes (Cp*2Co+)(H2Pc˙-)·0.5C6H4Cl2·0.7C6H5CN·0.3C6H14(1) and (Cp*2Cr+)(H2Pc˙-)·4C6H4Cl2(2) have been obtained as single crystals. Both complexes contain metal-free phthalocyanine (Pc) radical anions and decamethylmetallocenium cations. Reduction of the Pc macrocycle leads to the appearance of new bands at 1026-1030 nm in the NIR range and blue shifts of both Soret and Q-bands of H2Pc in the spectra of 1 and 2. The geometry of the Pc macrocycles supports the formation of H2Pc˙-by the alternation of shorter and longer C-N(imine) bonds in the macrocycles in 2. Complex 1 contains pairs of H2Pc˙-having effective π-π interactions with two sandwiched Cp*2Co+cations, whereas complex 2 contains stacks composed of alternating Cp*2Cr+and H2Pc˙-ions. The magnetic moment of 1 is 1.64 μBat 300 K due to the contribution of the H2Pc˙-spins with the S = 1/2 state and diamagnetism of Cp*2Co+. This is supported by the observation of a narrow EPR signal of 1 with g = 2.0032-2.0036 characteristic of H2Pc˙-. Strong antiferromagnetic coupling of spins with a Weiss temperature of -23 K is observed between H2Pc˙-in 1. This coupling is probably mediated by the Cp*2Co+cations. The magnetic moment of 2 is 4.18 μBat 300 K indicating the contribution of both paramagnetic H2Pc˙-(S = 1/2) and Cp*2Cr+(S = 3/2) species. In spite of the presence of stacks of alternating ions in 2, only weak magnetic coupling is observed with a Weiss temperature of -4 K most probably due to ineffective π-π interactions between Cp*2Cr+and H2Pc˙-. The EPR spectrum of 2 contains an asymmetric signal attributed to CrIII(g1= 3.9059-3.9220) and a narrow Lorentzian signal from H2Pc˙-with g2= 1.9943-1.9961. In addition to these signals, a broad EPR signal grows in intensity below 80 K with g4= 2.1085-2.2438 which can be attributed to both paramagnetic Cp*2Cr+and H2Pc˙-species having exchange interactions.
authors.affiliation: Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow Region, 142432 Russia. konarev3@yandex.ru.
authors.forename: Dmitri V
authors.identifier: http://orcid.org/0000-0002-7326-8118
authors.initials: DV
authors.lastname: Konarev
authors.affiliation: Institute of Solid State Physics RAS, Chernogolovka, Moscow Region, 142432 Russia.
authors.forename: Salavat S
authors.initials: SS
authors.lastname: Khasanov
authors.affiliation: Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan and Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
authors.forename: Manabu
authors.initials: M
authors.lastname: Ishikawa
authors.affiliation: Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan and Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
authors.forename: Akihiro
authors.initials: A
authors.lastname: Otsuka
authors.affiliation: Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan and Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
authors.forename: Hideki
authors.initials: H
authors.lastname: Yamochi
authors.affiliation: Faculty of Agriculture, Meijo University, 1-501 Shiogamaguchi, Tempaku-ku, Nagoya 468- 8502, Japan and Toyota Physical and Chemical Research Institute, 41-1, Yokomichi, Nagakute, Aichi 480-1192, Japan.
authors.forename: Gunzi
authors.initials: G
authors.lastname: Saito
authors.affiliation: Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow Region, 142432 Russia. konarev3@yandex.ru.
authors.forename: Rimma N
authors.initials: RN
authors.lastname: Lyubovskaya