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- Title
Features of Magnetic Behavior in the Row of Pentacoordinated Bis‐o‐Iminobenzosemiquinonato Metal (Al, Ga, In) Complexes.
- Authors
Ershova, Irina V.; Bogomyakov, Artem S.; Fukin, Georgy K.; Piskunov, Alexandr V.
- Abstract
The series of pentacoordinated bis‐o‐iminobenzosemiquinonato complexes with general formula (imSQ)2MR 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, N3, NCS) has been expanded through synthesis of six new (imSQ)2MR 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)2MR 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)2GaR 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)2MR 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)2InI (4). Group 13 metal bis‐o‐iminobenzosemiquinonates with general formula (imSQ)2MR have been investigated for factors influencing the magnetic exchange interactions between organic radicals in the coordination sphere of nontransition metals. In (imSQ)2GaR complexes the value of the magnetic exchange interaction depends linearly on the distance between the metal center and inorganic apical substituent.
- Subjects
METAL complexes; MAGNETIC properties of metals; IMINO compounds; RADICAL anions; SUBSTITUENTS (Chemistry)
- Publication
European Journal of Inorganic Chemistry, 2019, Vol 2019, Issue 7, p938
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201801348