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Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl 16 Pc} 2 ] 3– Dimers Containing [Fe I Cl 16 Pc(2–)] – and Diamagnetic [Fe 0 Cl 16 Pc(2–)] 2–
Author(s) -
Konarev Dmitri V.,
Kuzmin Alexey V.,
Ishikawa Manabu,
Nakano Yoshiaki,
Faraonov Maxim A.,
Khasanov Salavat S.,
Otsuka Akihiro,
Yamochi Hideki,
Saito Gunzi,
Lyubovskaya Rimma N.
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201400126
Subject(s) - chemistry , crystallography , dimer , inorganic chemistry , phthalocyanine , stereochemistry , organic chemistry
Iron hexadecachlorophthalocyanine (Cl 16 Pc) salts with a layered arrangement of phthalocyanine (Pc) macrocycles were obtained by the reduction of FeCl 16 Pc with sodium fluorenone ketyl in the presence of PPNCl [PPN + : bis(triphenylphosphine)iminium cation] and TBABr (TBA + : tetrabutylammonium cation). (PPN + )[(Fe I Cl 16 Pc) – ] · 0.78C 6 H 4 Cl 2 · 0.22C 6 H 14 ( 1 ) contains π–π stacking columns formed by dimerized (Fe I Cl 16 Pc) – anions. The side‐by‐side arrangement of neighboring columns results in the formation of a layered iron hexadecachlorophthalocyanine structure. (TBA + ) 3 {[(FeCl 16 Pc) 2 ] 3– } ( 2 ) contains hexagonal layers formed by [(FeCl 16 Pc) 2 ] 3– dimers and separated by TBA + cations. The dimers bear –3 charge and, according to optical and X‐ray diffraction data, consist of a [Fe I (Cl 16 Pc)] – monoanion and a [Fe 0 (Cl 16 Pc)] 2– dianion. These anions are bonded in the dimer by a Fe–Fe bond of 2.899(4) Å length. It was shown that the negative charge in both anions is localized on the iron atoms to form Fe I and Fe 0 , respectively, and no electron transfer to the hexadecachlorophthalocyanine macrocycles is observed. Magnetic data indicate the presence of only one S = 1/2 spin per [(FeCl 16 Pc) 2 ] 3– dimer. This result is in agreement with the formation of iron(I) and iron(0) hexadecachlorophthalocyanine anions, which have the iron atoms in d 7 and diamagnetic d 8 electron configuration, respectively. The spins of the iron(I) atoms are arranged in a hexagonal manner and only weakly interact, which results in a Weiss temperature of –1 K because of the long distances between them (>18 Å). Previously studied anionic salts with a columnar arrangement of [Fe I (Cl 16 Pc)] – do not show EPR signals from Fe I . In contrast, salt 2 shows an intense EPR signal with main components at g ⟂ = 2.249 and g ∥ = 1.989, which are characteristic of Fe I with d 7 electron configuration.