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Features of Magnetic Behavior in the Row of Pentacoordinated Bis‐ o ‐Iminobenzosemiquinonato Metal (Al, Ga, In) Complexes
Author(s) -
Ershova Irina V.,
Bogomyakov Artem S.,
Fukin Georgy K.,
Piskunov Alexandr V.
Publication year - 2019
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.201801348
Subject(s) - chemistry , superexchange , crystallography , antiferromagnetism , metal , stereochemistry , substituent , pyridine , radical , molecule , ion , medicinal chemistry , physics , organic chemistry , condensed matter physics
The series of pentacoordinated bis‐ o ‐iminobenzosemiquinonato complexes with general formula (imSQ) 2 MR where imSQ – is a radical anion of 4,6‐di‐ tert ‐butyl‐ N ‐(2,6‐di‐isopropylphenyl)‐ o ‐iminobenzoquinone (M = Al, Ga, In; R = Akl, Hal, N 3 , NCS) has been expanded through synthesis of six new (imSQ) 2 MR complexes [M = In, R = Me ( 1 ), Br ( 5 ), Cl ( 6 ); M = Ga, R = OPh ( 16 ), NCO ( 17 ); M = Al, R = NCO ( 23 )]. In all complexes (imSQ) 2 MR except for R = Alk the strong antiferromagnetic exchange coupling between organic radicals, conditioned by the presence of the pathway for superexchange, takes place. In the (imSQ) 2 GaR complexes the value of magnetic exchange interaction ( J ) was found to depend linearly on the distance between metal center and inorganic apical substituent: the shortening of Ga–R distance in the row Ga–I > Ga–Br > Ga–Cl > Ga–NCS > Ga–OPh is accompanied by the increasing of J value from –68.6 to –139.3 cm –1 . For Al and In analogues complexes such dependence has not been observed. The pathway for superexchange in pentacoordinated (imSQ) 2 MR complexes was found to be broken after complex coordination geometry changeover to hexacoordinated one, which was clearly demonstrated by the example of pyridine molecule coordination to the (imSQ) 2 InI ( 4 ).