title: Molecular structure, optical and magnetic properties of metal-free phthalocyanine radical anions in crystalline salts (H2Pc˙-)(cryptand[2,2,2][Na(+)])·1.5C6H4Cl2 and (H2Pc˙-)(TOA+)·C6H4Cl2 (TOA+ is tetraoctylammonium cation).
abstract: Ionic compounds containing radical anions of metal-free phthalocyanine (H2Pc˙(-)): (H2Pc˙(-))(cryptand[2,2,2][Na(+)])·1.5C6H4Cl2 (1) and (H2Pc˙(-))(TOA(+))·C6H4Cl2 (2) have been obtained as single crystals for the first time. Their crystal structures have been determined, and optical and magnetic properties have been investigated. The H2Pc˙(-) radical anions have a slightly bowl-like shape with four pyrrole nitrogen atoms located below the molecular plane, while four phenylene substituents are located above this plane. Changes in the average length of N-C and C-C bonds in H2Pc˙(-) in comparison with those in neutral H2Pc indicate that negative charge is mainly delocalized over the 24-atom phthalocyanine ring rather than the phenylene substituents. The H2Pc˙(-) formation is accompanied by a shift of up to 10 cm(-1) and disappearance of some intense IR-active bands whereas the band of the N-H stretching mode is shifted by 21-27 cm(-1) to larger wavenumbers. New bands attributed to H2Pc˙(-) appear in the NIR spectra of the salts with maxima at 1033 and 1028 nm for 1 and 2, respectively. The formation of H2Pc˙(-) is accompanied by the splitting of the Soret and Q-bands of H2Pc into several bands and their blue-shift up to 32 nm. Narrow EPR signals with g = 2.0033 and linewidth of 0.16-0.24 mT at room temperature in the spectra of the salts were attributed to the H2Pc˙(-) radical anions. According to SQUID measurements they have S = 1/2 spin states with effective magnetic moments of 1.73 (1) and 1.78 (2) μB at 300 K. Magnetic behavior of 1 and 2 follows the Curie-Weiss law with negative Weiss temperatures of -0.9 and -0.5 K, respectively, indicating weak antiferromagnetic interactions of spins. The EPR signal splits into two lines below 120 and 80 K for 1 and 2, respectively and these lines are noticeably broadened below 25 K.
authors.affiliation: Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432 Russia. konarev@icp.ac.ru
authors.forename: Dmitri V
authors.initials: DV
authors.lastname: Konarev
authors.forename: Leokadiya V
authors.initials: LV
authors.lastname: Zorina
authors.forename: Salavat S
authors.initials: SS
authors.lastname: Khasanov
authors.forename: Aleksey L
authors.initials: AL
authors.lastname: Litvinov
authors.forename: Akihiro
authors.initials: A
authors.lastname: Otsuka
authors.forename: Hideki
authors.initials: H
authors.lastname: Yamochi
authors.forename: Gunzi
authors.initials: G
authors.lastname: Saito
authors.forename: Rimma N
authors.initials: RN
authors.lastname: Lyubovskaya