Coordination Complexes of a Neutral 1,2,4-Benzotriazinyl Radical Ligand: Synthesis, Molecular and Electronic Structures, and Magnetic Properties.
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.
Department of Chemistry, Nanoscience Center, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä (Finland). ian.s.morgan@jyu.fi.
Ian S
IS
Morgan
Department of Chemistry, Nanoscience Center, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä (Finland).
Akseli
A
Mansikkamäki
Department of Chemistry, University of Cyprus, P.O. Box 20537, 1678 Nicosia (Cyprus).
Georgia A
GA
Zissimou
Department of Chemistry, University of Cyprus, P.O. Box 20537, 1678 Nicosia (Cyprus).
Panayiotis A
PA
Koutentis
CNRS, CRPP, UPR 8641, 33600 Pessac (France).|Univ. Bordeaux, CRPP, UPR 8641, 33600 Pessac (France).
Mathieu
M
Rouzières
CNRS, CRPP, UPR 8641, 33600 Pessac (France).|Univ. Bordeaux, CRPP, UPR 8641, 33600 Pessac (France).
Rodolphe
R
Clérac
Department of Chemistry, Nanoscience Center, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä (Finland). heikki.m.tuononen@jyu.fi.
Heikki M
HM
Tuononen
exchange interactions; heterocycles; magnetic properties; metal-radical interactions; radicals