Atomically Precise Lanthanide‐Iron‐Oxo Clusters Featuring the ϵ‐Keggin Ion

Abstract

Atomically precisem olecular metal-oxo clusters provide ideal modelst ou nderstand metal oxide surfaces, self-assembly,a nd form-function relationships. Devising strategies for synthesis and isolation of these molecular forms remains ac hallenge. Here, the synthesis of four Ln-Fe oxo clusters that feature the e-{Fe 13 }K egginc luster in their core is reported.T he {Fe 13 }m etal-oxo cluster motif is the building block of two important iron oxyhydroxyide phases in nature and technology,f errihydrite (as the d-isomer) and magnetite (the e-isomer). The reported e-{Fe 13 }K eggin isomer as an isolated molecule provides the opportunity to study the formation of ferrihydrite andm agnetite from this building unit. The four currently reported isostructural lanthanide-iron-oxo clusters are fully formulated [Y 12 Fe 33 (TEOA) 12 (Hyp) 6 (m 3 -OH) 20 (m 4 -O) 28 (H 2 O) 12 ](ClO 4 ) 23 ·50 H 2 O (1, Y 12 Fe 33 ), [Gd 12 Fe 33 (TEOA) 12 (Hyp) 6 (m 3 -OH) 20 (m 4 -O) 32 (H 2 O) 12 ]-(ClO 4 ) 15 ·50 H 2 O( 2, Gd 12 Fe 33 )a nd [Ln 16 Fe 29 (TEOA) 12 (Hyp) 6 (m 3 -OH) 24 (m 4 -O) 28 (H 2 O) 16 ](ClO 4 ) 16 (NO 3 ) 3 ·n H 2 O( Ln = Yf or 3, Y 16 Fe 29 , n = 37 and Ln = Gd for 4, Gd 16 Fe 29 n = 25;H yp = trans-4-Hydroxyl-l-proline and TEOA = triethanolamine). The next metal layer surrounding the e-{Fe 13 }c ore within thesec lusters exhibits as imilara rrangement as the magnetite lattice, and Fe and Ln can occupy the same positions. This provides the opportunity to construct af amily of compounds and optimize magnetic exchange in these molecules through compositiont uning.S mall-angle X-ray scattering (SAXS) and high-resolution electrosprayi onizationm ass spectrometry (HRESI-MS) show that these clusters are stable upon dissolution in both water ando rganic solvents, as af irst step to performing further chemistry towardsb uildingm agnetic arrays or investigating ferrihydrite and magnetite assembly from pre-nucleation clusters.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Soft Metal–Organic Frameworks Based on {Na@Ln6} as a Secondary Building Unit Featuring a Magnetocaloric Effect and Fluorescent Sensing for Cyclohexane and Fe3+

“…EDTA 4– displays two kinds of different coordination modes in compounds 1 – 2 and 3 – 4 , respectively (Figure S4). In compound 1 , the bond distances of Gd–O and Gd–N are 2.3378–2.5347 Å and 2.6211–2.7141 Å, and the bond distances of Gd–O and Gd–N are 2.3351–2.8501 Å and 2.6202–2.7051 Å in compound 4 , respectively, consisting of the previously reported Gd-containing complexes. , …”

Multi-Nuclear Rare-Earth-Implanted Tartaric Acid-Functionalized Selenotungstates and Their Fluorescent and Magnetic Properties

“…Noteworthily, inserting RE ions to POMs has become a crucial domain in supramolecular chemistry, in which the resulting RE-inserted POM units are able to be interacted with by H-bonding or van der Waals interactions. So, the generated three-dimensional supramolecular frameworks may be considered as promising candidates for use in chemical biology, materials chemistry, etc. − H-bonding interactions between nitrogen atoms of H 2 tart 2– ligands and between oxygen atoms of ST subunits and water molecules lead to a three-dimensional supramolecular structure of 1 with N–H···O distances of 2.97(4)–3.21(4) Å and O–H···O distances of 2.89(4)–3.27(4) Å.…”

A Giant 3d‐4f Polyoxometalate Super‐Tetrahedron with High Proton Conductivity

“…Their nanoscale sizes and high metal numbers provide a bridge between the quantum and classical worlds, and offer the potential for the discovery of new physical phenomena. [ 1–11 ] A particularly fascinating area in this field is the high‐nuclearity heterometallic 3d‐4f clusters because of their interesting properties arising from the interactions of 3d and 4f metal ions. [ 8–16 ] Due to involving a large number of molecules and the variable coordination geometry of lanthanide ions, the assembly of high‐nuclearity 3d‐4f clusters is a challenging topic.…”

“…Until now, several gigantic heterometallic 3d‐4f clusters have been obtained under the protection of organic ligands. [ 9–15 ] Although organic ligand can regulated the final cluster structures, the relatively low structural and thermal stability of the clusters may prevent further related property studies. In comparison, the inorganic anions with multisite coordination geometry can obviously improve the stability.…”