title: Synthesis, characterization, and electrochemical properties of a series of sterically varied iron(II) alkoxide precursors and their resultant nanoparticles.
abstract: A new family of iron(II) aryloxide [Fe(OAr)(2)(py)(x)] precursors was synthesized from the alcoholysis of iron(II) mesityl [Fe(Mes)(2)] in pyridine (py) using a series of sterically varied 2-alkyl phenols (alkyl = methyl (H-oMP), isopropyl (H-oPP), tert-butyl (H-oBP)) and 2,6-dialkyl phenols (alkyl = methyl (H-DMP), isopropyl (H-DIP), tert-butyl (H-DBP), phenyl (H-DPhP)). All of the products were found to be mononuclear and structurally characterized as [Fe(OAr)(2)(py)(x)] (x = 3 OAr = oMP (1), oPP (2), oBP (3), DMP (4), DIP (5); x = 2 OAr = DBP (6), DPhP (7)). The use of tris-tert-butoxysilanol (OSi(OBu(t))(3) = TOBS) led to isolation of [Fe(TOBS)(2)(py)(2)] (8). The new Fe(OAr)(2)(py)(x) (1-6) were found, under solvothermal conditions, to produce nanodots identified by PXRD as the γ-maghemite phase. The model precursor 3 and the nanoparticles 6n were evaluated using electrochemical methods. Cyclic voltammetry for 3 revealed multiple irreversible oxidation peaks, which have been tentatively attributed to the loss of alkoxide ligand coupled with the deposition of a solid Fe-containing coating on the electrode. This coating was stable out to the voltage limits for the acetonitrile solvent.
authors.affiliation: Sandia National Laboratories, Advanced Materials Laboratory, 1001 University Boulevard, Southeast, Albuquerque, New Mexico 87106, USA. tjboyle@Sandia.gov
authors.forename: Timothy J
authors.initials: TJ
authors.lastname: Boyle
authors.forename: Leigh Anna M
authors.initials: LA
authors.lastname: Ottley
authors.forename: Christopher A
authors.initials: CA
authors.lastname: Apblett
authors.forename: Constantine A
authors.initials: CA
authors.lastname: Stewart
authors.forename: Sarah M
authors.initials: SM
authors.lastname: Hoppe
authors.forename: Krista L
authors.initials: KL
authors.lastname: Hawthorne
authors.forename: Mark A
authors.initials: MA
authors.lastname: Rodriguez
mesh_terms: D018360:Crystallography, X-Ray; D004563:Electrochemistry; D005296:Ferrous Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D008958:Models, Molecular; D053758:Nanoparticles / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D010316:Particle Size; D013499:Surface Properties
chemical_list: D005296:Ferrous Compounds; D010087:Oxides