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

Abstract

The syntheses, crystal structures, and physical properties of [HFe19 O14 (OEt)30 ] and {Fe11 (OEt)24 }∞ are reported. [HFe19 O14 (OEt)30 ] has an octahedral shape. Its core with a central Fe metal ion surrounded by six μ6 -oxo ligands is arranged in the rock salt structure. {Fe11 (OEt)24 }∞ is a mixed-valence coordination polymer in which Fe(III) metal ions form three 3D interpenetrating (10,3)-b nets. The arrangement of the Fe(III) ions can also be compared to that of Si ions in α-ThSi2 . Thus, the described structures are at the interface between molecular and solid-state chemistry.

Tuning the Condensation Degree of {FeIIIn} Oxo Clusters via Ligand Metathesis, Temperature, and Solvents

“…All Fe III atoms in 1 are six-coordinated and adopt an elongated octahedral O 5 Cl environment by a terminal chloride and five oxygen atoms: one central μ 6 -O atom and four O atoms from two neighboring thme 3– ligands (Fe–(μ 6 -O): 2.223­(1)–2.264­(11), other Fe–O: 1.978(7)–2.005(8), Fe–Cl: 2.266(5)–2.292(3) Å; Table ). The similar octahedral {Fe 6 (μ 6 -O)} unit with a central μ 6 -oxo group was previously found in other hexanuclear Fe III complexes, where the role of cations play sodium, hydroxonium, tetramethylamonium, or pyridinium, as well as in several higher nuclearity complexes such as hepta-, dodeca-, and nonadecanuclear iron aggregates.…”

Versatile Organic Chemistry on Vanadium‐Based Multi‐Electron Reservoirs

“…Many structures can coexist in solution in dynamic equilibria. This makes classical POM chemistry in aqueous media hard to predict …”

“…[1][2][3] Since this class of compounds exhibits av ast structural diversity,t ransition-metal oxide clusters of precisely defined size, shape, and composition can be tailor-made to serve a specific purpose.T heir propertiesd epend mainly on the structure and compositiono ft he metal-oxygen framework, butc an be tuned and extended by organic functionalization. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] An established functionalizationm ethod is to use derivatives of the tripodala lcohol tris(hydroxymethyl)methane with the formula (HOCH 2 ) 3 CÀR( "H 3 trisÀR'')t oi ntroduce organic moieties (R) to the POMs. [19] Lindqvist-, Dawson-, or Anderson-type structuresa re the most prominente xamples in which this functionalization strategyh as successfully been employed.…”

“…This makes classical POM chemistry in aqueous media hard to predict. [5,8] Hartl et al reportedt he synthesis of neutral Lindqvist-type vanadium compounds[ V 6 O 7 (OR) 12 ](R= Me, Et) with acomplete organic shell. [9,10] They are soluble in almosta ll common solvents ranging from pure hexanes to pure methanolt om ixtures of water with organic solvents.…”

“…Since this class of compounds exhibits a vast structural diversity, transition‐metal oxide clusters of precisely defined size, shape, and composition can be tailor‐made to serve a specific purpose. Their properties depend mainly on the structure and composition of the metal–oxygen framework, but can be tuned and extended by organic functionalization …”