The Salts of Copper Octafluoro- and Hexadecafluorophthalocyanines Containing [CuII(F8Pc)4-]2-Dianions and [CuF16Pc]-Monoanions.
Crystalline anionic salts with copper octafluoro- and hexadecafluorophthalocyanines, (Bu4N+)2[CuII(F8Pc)4-]2-·2C6H4Cl2(1) and (PPN+)3[CuF16Pc]33-·2C6H5CN (2), where PPN+is bis(triphenylphosphoranylidene)ammonium and Pc is phthalocyanine, have been obtained. The absence of noticeable absorption in the NIR range and DFT calculations for 1 indicate that both negative charges are mainly localized on the Pc ligand, and that the [CuII(F8Pc)4-]2-dianions are formed without reduction of CuII. The magnetic moment of 1.60 μBcorresponds to the contribution of one S = 1/2 spin per dianion. The spin is localized on the CuIIatom, which shows an EPR signal characteristic of CuII. Dianions are isolated in 1, providing only weak magnetic coupling of spins with a Weiss temperature of -4 K. Salt 2 contains closely packed π-π stacks built of [CuF16Pc]-anions of types I and II, and the interplanar distances are 3.187 and 3.275 Å. According to the DFT calculations, the [CuF16Pc]-anions of types I and II can have different charge distributions, with localization of an extra electron on the copper atoms to form diamagnetic [CuI(F16Pc)2-]-monoanions or delocalization of an extra electron on the F16Pc ligand to form [CuII(F16Pc)•3-]•-having an S = 1/2 (CuII) + 1/2 (F16Pc•3-) spin state. In fact, at 300 K, the magnetic moment of 2 of 3.25 μBper formula unit is rather close to the contribution from two [CuII(F16Pc)•3-]•-(calculated μeffis 3.46 μB). The Weiss temperature of -21.5 K indicates antiferromagnetic coupling of spins, which can be modeled by stronger intermolecular coupling between (F16Pc)•3-with J1/kB= -23.5 K and weaker intramolecular coupling between CuIIand (F16Pc)•3-with J2/kB= -8.1 K. This interaction is realized in the {[CuII(F16Pc)•3-]•-}2dimers separated by diamagnetic [CuI(F16Pc)2-]-species. In spite of the stacking arrangement of phthalocyanine macrocycles in 2, the inhomogeneous charge distribution and nonuniform distances between the macrocycles should suppress electrical conductivity.
Institute of Problems of Chemical Physics RAS , Chernogolovka, Moscow Region, 142432 Russia.
Dmitri V
http://orcid.org/0000-0002-7326-8118
DV
Konarev
Chemistry Department, Moscow State University , Leninskie Gory,119991 Moscow, Russia.
Sergey I
http://orcid.org/0000-0003-1663-0341
SI
Troyanov
Institute of Solid State Physics RAS , Chernogolovka, Moscow Region, 142432 Russia.
Alexey V
AV
Kuzmin
Division of Chemistry, Graduate School of Science, Kyoto University , Sakyo-ku, Kyoto 606-8502, Japan.
Yoshiaki
Y
Nakano
Division of Chemistry, Graduate School of Science, Kyoto University , Sakyo-ku, Kyoto 606-8502, Japan.|Research Center for Low Temperature and Materials Sciences, Kyoto University , Sakyo-ku, Kyoto 606-8501, Japan.
Manabu
M
Ishikawa
Institute of Problems of Chemical Physics RAS , Chernogolovka, Moscow Region, 142432 Russia.
Maxim A
MA
Faraonov
Institute of Solid State Physics RAS , Chernogolovka, Moscow Region, 142432 Russia.
Salavat S
SS
Khasanov
Institute of Problems of Chemical Physics RAS , Chernogolovka, Moscow Region, 142432 Russia.
Alexey L
AL
Litvinov
Division of Chemistry, Graduate School of Science, Kyoto University , Sakyo-ku, Kyoto 606-8502, Japan.
Akihiro
A
Otsuka
Division of Chemistry, Graduate School of Science, Kyoto University , Sakyo-ku, Kyoto 606-8502, Japan.
Hideki
H
Yamochi
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.
Gunzi
G
Saito
Institute of Problems of Chemical Physics RAS , Chernogolovka, Moscow Region, 142432 Russia.
Rimma N
RN
Lyubovskaya