Symmetrievarianten bei vielkernigen Mangan‐Oxo‐Clustern mit hohem Spinzustand: supramolekulare Synthese von Kepleraten und chiralen Festkörpern auf Mangan‐Basis

Abstract

Koordinationscluster: Eine supramolekulare Synthese mit Chloridionen als strukturbestimmenden Liganden ergibt gemischtvalente Mn‐Koordinationscluster der Zusammensetzungen {MnIIMnIII12}, {MnII3MnIII10} und {MnII3MnIII11} mit supramolekularer Chiralität. Der {MnIIMnIII12}‐Komplex (siehe Bild; Mn blau, Cl grün, O rot), das erste strukturell charakterisierte Keplerat auf Mn‐Basis, weist eine der höchsten bisher in Mn‐Koordinationsclustern bekannten Symmetrien auf.

17O NMR chemical shifts in oxometalates: from the simplest monometallic species to mixed-metal polyoxometalates

“…Polyoxometalates (or POMs) are discrete early transition metal oxides assembled from corner-, edge-and face-sharing [MO x ] units, with x = 4-7 and typically M = W VI , Mo VI , V V , Nb V or Ta V . [1][2][3][4][5][6][7] Several polyanions made of U VI , 8 Sb V , 9 and Mn II/III , 10 as well as late transition metals such as Pd II , Pt III and Au III , [11][12][13][14][15][16] are also known. The versatility of POMs is extraordinary; they conform a family of inorganic compounds with unmatched tunable physical and inorganic properties.…”

Hetero‐Epitaxial Approach by Using Labile Coordination Sites to Prepare Catenated Metal–Organic Frameworks with High Surface Areas

“…[11] Herein, we report a series of unprecedented MOFs, highly augmented topologies of which give rise to very high-surface areas. In line with our expertise, [12] we apply a coordinationchemistry approach that demonstrates how kinetically labile binding sites can be exploited to modify MOF topologies that have the tendency to form interwoven assemblies, generating cross-linked 3D catenane structures. Synthetic approaches to catenanes and rotaxanes predominately rely on template effects, which facilitate the prearrangement of molecular components prior to the final ring closure.…”

Directed Synthesis of {Mn18Cu6} Heterometallic Complexes

“…However, none of these one-pot reactions result in either similar metal ion topologies or oxidation levels to those found in 2 and 3 . Interestingly, the {Mn III 12 } core structure of the {Mn 18 Cu 6 } complexes is related to the smaller Mn-oxo clusters, [Mn IV Mn III 6 Mn II 6 O 8 (OEt) 6 (O 2 CPh) 12 ]17 and [Mn II Mn III 12 (μ 4 -O) 8 (μ 4 -Cl) 6 ( t Bu-PO 3 ) 8 ]18 where the central position is occupied by a Mn IV or a Mn II cation, respectively (cf. empty in 2 and 3 ).…”