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Magnetic Exchange through the Dianionic Hexaazatrinaphthylene (HATNA) Ligand in {HATNA(Fe II Cl 2 ) 3 } 2− Containing Fe II ( S =2) Triangles
Author(s) -
Konarev Dmitri V.,
Khasanov Salavat S.,
Mikhailenko Maxim V.,
Batov Mikhail S.,
Shestakov Alexander F.,
Kuzmin Alexey V.,
Otsuka Akihiro,
Yamochi Hideki,
Kitagawa Hiroshi,
Lyubovskaya Rimma N.
Publication year - 2021
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.202000946
Subject(s) - chemistry , antiferromagnetism , crystallography , diamagnetism , cationic polymerization , ligand (biochemistry) , magnetic susceptibility , crystal structure , equilateral triangle , stereochemistry , magnetic field , condensed matter physics , physics , biochemistry , geometry , mathematics , receptor , organic chemistry , quantum mechanics
Herein, a new method for the preparation of anionic hexaazatrinaphthylene (HATNA) coordination complexes was developed. The reduced HATNA coordinated three Fe II Cl 2 units for the formation of (CV + ) 2 {HATNA(Fe II Cl 2 ) 3 } 2− ⋅ 3.5 C 6 H 4 Cl 2 ( 1 ) (CV + is a cationic form of crystal violet). The Fe II atoms had a high S =2 spin state and were arranged in nearly equilateral triangles at a distance of approximately 7 Å. The χ M T value of 1 was 9.70 emu⋅K/mol at 300 K, exceeding the calculated spin‐only value of three independent high‐spin Fe II centers ( S =2) (9.00 emu⋅K/mol). A strong antiferromagnetic exchange was observed between Fe II atoms through the diamagnetic HATNA units since Weiss temperature is −98 K. Magnetic behavior of 1 was modelled by PHI package obtaining the exchange interaction constant J =−4.6 cm −1 and zero‐field splitting parameter D =5.6 cm −1 at g =2.23. Arrangement of magnetic centers in the equilateral triangles supposes that some degree of spin frustration exists in 1 . Crystal structures of two phases of pristine HATNA molecule are also reported.