{Fe6O2}-Based Assembly of a Tetradecanuclear Iron Nanocluster

Abstract

The tetradecanuclear FeIII pivalate nanocluster [Fe14O10(OH)4(Piv)18], comprising a new type of metal oxide framework, has been solvothermally synthesized from a hexanuclear iron pivalate precursor in dichlormethane/acetonitrile solution. Magnetic measurements indicate the presence of very strong antiferromagnetic interactions in the cluster core.

Ba4KFe3O9: A Novel Ferrite Containing Discrete 6-Membered Rings of Corner-Sharing FeO4 Tetrahedra

“…A similar effect was observed for [Fe 14 O 10 (OH) 4 (Piv) 18 ] where the room temperature moment was only about 20% of the spin-only value. 14 …”

“…10 Furthermore, when such rings contain magnetic ions, such as manganese, molybdenum or iron, they typically exhibit complex magnetic interactions. 11 Over the years, a number of iron containing molecular ring structures, referred to as ferric wheels, 12,13 have been crystallized via solution routes, including [Fe(OMe) 2 (O 2 CCH 2 Cl)] 10 , 13 [Fe 14 O 10 (OH) 4 (Piv) 18 (HPiv = pivalic acid) 14 and [Fe(OH)(C 30 H 38 N 2 O 8 )Fe 2 (OCH 3 04(O 2 CCH 3 ) 2 ]6. 15 …”

[Fe19] “Super‐Lindqvist” Aggregate and Large 3D Interpenetrating Coordination Polymer from Solvothermal Reactions of [Fe2(OtBu)6] with Ethanol

“…Tables S2 and S3), [33] ATR-FT-IR ( Figures S2-S6), and Mçssbauer studies (Figures S7-S9) did not provide any indication for the presence of Fe II .T hus,o ne oxo or one ethoxo group has to be protonated for charge balance. [34] Moreover,I Rs pectroscopic studies point to as ignificant intramolecular proton transfer between m 3 -oxo groups and ethoxo ligands (Supporting Information, Figures S2-S6). Therefore,t he formula of this new aggregate should be [Fe 19…”

“…[34] Moreover,I Rs pectroscopic studies point to as ignificant intramolecular proton transfer between m 3 -oxo groups and ethoxo ligands (Supporting Information, Figures S2-S6 Figure 2A) exhibits an approximate O h symmetry.T he aggregate comprises six m 6 -oxo groups that surround the central iron site in anearly perfect octahedral manner ( Figure 2D). Its structure can be considered as a3 De xtract from the rock salt or Wüstite lattice ( Figure 2B,C).…”

Ein [Fe19]‐“Super‐Lindqvist”‐Aggregat und ein großes, sich durchdringendes, dreidimensionales Koordinationspolymer aus Solvothermalreaktionen von [Fe2(OtBu)6] mit Ethanol

“…Da Va lenzsummenberechnungen (Tabellen S2 und S3 der SI) [33] sowie ATR-FT-IR-(Abbildungen S2-S6 der SI) und Mçßbauer-spektroskopische Untersuchungen (Abbildungen S7-S9 der SI) das Vorhandensein von Fe II -Ionen ausschließen, muss zum Ausgleichen der Ladungsbilanz eine Oxo-oder eine Ethoxo-Gruppe protoniert sein. [34] Diese Hypothese wird durch IR-spektroskopische Untersuchungen bestätigt, die darüber hinaus auf einen intramolekularen Protonentransfer zwischen den m 3 -Oxo-und den Ethoxo-Gruppen schließen 6 ]-Einheit. [35] So gesehen ist diese interessante ionische Verbindung keine korrekte Erweiterung der Lindqvist-Architektur und muss daher als beispiellose,e igenständige Polyoxometallatstruktura ngesehen werden.…”