title: Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato-Anions and Indium(III) Phthalocyanine Bromide Radical Anions.
abstract: Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu4N+)2[MIII(HFl-O-)(Pc.3-)].-(Br-)⋅1.5 C6H4Cl2[M=Al (1), Ga (2); HFl-O-=fluoren-9-olato-anion; Pc=phthalocyanine] and (Bu4N+) [InIIIBr(Pc.3-)].-⋅0.875 C6H4Cl2⋅0.125 C6H14(3). The salts were found to contain Pc.3-radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc.3-in the near-IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl-O-anions in 1 and 2 with short Al-O and Ga-O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C-O bonds [1.402(3) and 1.391(11) Å in 1 and 2, respectively] in the HFl-O-anions are longer than the same bond in the fluorenone ketyl (1.27-1.31 Å). Salts 1-3 show effective magnetic moments of 1.72, 1.66, and 1.79 μBat 300 K, respectively, owing to the presence of unpaired S=1/2 spins on Pc.3-. These spins are coupled antiferromagnetically with Weiss temperatures of -22, -14, and -30 K for 1-3, respectively. Coupling can occur in the corrugated two-dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J/kB=-0.9 and -1.1 K, respectively, and in the π-stacking {[InIIIBr(Pc.3-)].-}2dimers of 3 with an exchange interaction of J/kB=-10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc.3-. It was found that increasing the size of the central metal atom strongly broadened these EPR signals.
authors.affiliation: Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432, Russia.
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: 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: Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto, 606-8501, Japan.|Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
authors.forename: Yoshiaki
authors.initials: Y
authors.lastname: Nakano
authors.affiliation: Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto, 606-8501, Japan.|Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
authors.forename: Akihiro
authors.initials: A
authors.lastname: Otsuka
authors.affiliation: Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto, 606-8501, Japan.|Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, 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.|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.
authors.forename: Rimma N
authors.initials: RN
authors.lastname: Lyubovskaya
keywords: aluminum; antiferromagnetic coupling; gallium; indium; magnetic properties; phthalocyanines; radical ions