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Coordination Complexes of a Neutral 1,2,4‐Benzotriazinyl Radical Ligand: Synthesis, Molecular and Electronic Structures, and Magnetic Properties
Author(s) -
Morgan Ian S.,
Mansikkamäki Akseli,
Zissimou Georgia A.,
Koutentis Panayiotis A.,
Rouzières Mathieu,
Clérac Rodolphe,
Tuon Heikki M.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201501343
Subject(s) - ligand (biochemistry) , crystallography , antiferromagnetism , chemistry , unpaired electron , magnetic susceptibility , metal , octahedron , radical ion , ferromagnetism , electron configuration , crystal structure , stereochemistry , ion , molecule , condensed matter physics , physics , organic chemistry , biochemistry , receptor
A series of d‐block metal complexes of the recently reported coordinating neutral radical ligand 1‐phenyl‐3‐(pyrid‐2‐yl)‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl ( 1 ) was synthesized. The investigated systems contain the benzotriazinyl radical 1 coordinated to a divalent metal cation, Mn II , Fe II , Co II , or Ni II , with 1,1,1,5,5,5‐hexafluoroacetylacetonato (hfac) as the auxiliary ligand of choice. The synthesized complexes were fully characterized by single‐crystal X‐ray diffraction, magnetic susceptibility measurements, and electronic structure calculations. The complexes [Mn( 1 )(hfac) 2 ] and [Fe( 1 )(hfac) 2 ] displayed antiferromagnetic coupling between the unpaired electrons of the ligand and the metal cation, whereas the interaction was found to be ferromagnetic in the analogous Ni II complex [Ni( 1 )(hfac) 2 ]. The magnetic properties of the complex [Co( 1 )(hfac) 2 ] were difficult to interpret owing to significant spin–orbit coupling inherent to octahedral high‐spin Co II metal ion. As a whole, the reported data clearly demonstrated the favorable coordinating properties of the radical 1 , which, together with its stability and structural tunability, make it an excellent new building block for establishing more complex metal–radical architectures with interesting magnetic properties.