title: Halide Influence on Molecular and Supramolecular Arrangements of Iron Complexes with a 3,5-Bis(2-Pyridyl)-1,2,4,6-Thiatriazine Ligand.
abstract: A series of iron centered complexes, namely, [Fe(Py2TTA)Cl2] (1), [Fe(Py2TTA)Br2] (2), and [Fe(μ-F)(Py2TTAO)F]∞ (3), were isolated via complexation of 3,5-bis(2-pyridyl)-1,2,4,6-thiatriazine (Py2TTAH) with various ferric halides (e.g., FeF3, FeCl3, and FeBr3). Comparison of the optical and electrochemical spectroscopy, structural analysis, and magnetic studies reveal numerous similarities between the chlorido (1) and bromido (2) derivatives, which crystallize as discrete five-coordinate iron centered complexes with coordination geometries that are intermediate between trigonal bipyramidal and square base pyramid. Conversely, the fluorido derivative (3) results in a completely different structure due to oxidation of the ligand and the formation of a one-dimensional coordination polymer held together through a bridging fluoride ion. Consequently, the spectroscopic and magnetic behavior of 3 differs significantly compared with 1 and 2. Complexes 1 and 2 exhibit paramagnetic properties typical for a mononuclear S = 5/2 system with weak intermolecular antiferromagnetic interactions at low temperatures, whereas complex 3 demonstrates significant exchange couplings within the chain and weak antiferromagnetic interchain interactions, which stabilize a canted antiferromagnetic state below 4.2 K.
authors.affiliation: Department of Chemistry and Biomolecular Science, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Katie L M
authors.initials: KL
authors.lastname: Harriman
authors.affiliation: Department of Chemistry and Biomolecular Science, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Irina A
authors.initials: IA
authors.lastname: Kühne
authors.affiliation: Department of Chemistry and Biomolecular Science, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Alicea A
authors.initials: AA
authors.lastname: Leitch
authors.affiliation: Department of Chemistry and Biomolecular Science, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Ilia
authors.initials: I
authors.lastname: Korobkov
authors.affiliation: CNRS, CRPP , UPR 8641, F-33600 Pessac, France.|Univ. Bordeaux, CRPP , UPR 8641, F-33600 Pessac, France.
authors.forename: Rodolphe
authors.initials: R
authors.lastname: Clérac
authors.affiliation: Department of Chemistry and Biomolecular Science, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Muralee
authors.initials: M
authors.lastname: Murugesu
authors.affiliation: Department of Chemistry and Biomolecular Science, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Jaclyn L
authors.initials: JL
authors.lastname: Brusso