Die organische Funktionalisierung von Polyoxovanadaten: Sb‐N‐Bindungen und Ladungskontrolle

Abstract

Neue Anknüpfungspunkte: Unter hydrothermalen Bedingungen geknüpfte kovalente Sb‐N‐Bindungen ermöglichen die Anbindung primärer und sekundärer organischer Amine (C grau, N blau) an existierende Antimonato‐Polyoxovanadat‐Clusteranionen (in Polyederdarstellung; O rot, Sb gelb), deren Ladung durch protonierte Amine kompensiert werden kann.

Synthesis, Structure, and Solubility Studies of a New Arsenato‐Polyoxovanadate Cluster Compound: (NH4)4[V12As8O40(H2O)]·4H2O

“…In antimonato POV structures often relatively short intercluster Sb ··· O separations (ca. 2.7–3 Å) are observed 41–44. In case of compound 1 the shortest As ··· O distance between neighbored clusters is 3.047 Å, which is shorter than the sum of the van der Waals radii of arsenic and oxygen (3.37 Å) but obviously larger than reported for antimony POVs.…”

“…and chemically modified POVs. we have recently isolated several chemically modified polyoxovanadates, namely (C 6 H 17 N 3 )[V 16 Sb 4 O 42 ] · 2H 2 O, (NH 4 ) 4 [V 14 Sb 8 O 42 ] · 2H 2 O,41 (trenH 3 ) 2 [V 15 Sb 6 O 42 ] · n H 2 O42 (tren = tris(2‐aminoethyl)amine), [V 16 Sb 4 O 42 (H 2 O){VO(C 6 H 14 N 3 ) 2 } 4 ] · 10H 2 O · C 6 H 14 N 2 43 (C 6 H 14 N 2 = (±)‐trans‐1,2‐diaminocyclohexane), [V 14 Sb 8 (C 6 H 15 N 3 ) 4 O 42 (H 2 O)] · 4H 2 O,(C 6 H 17 N 3 ) 2 [V 15 Sb 6 (C 6 H 15 N 3 ) 2 O 42 (H 2 O)] · 2.5H 2 O,44 (aepH 3 ) 4 [V 14 Ge 8 O 50 ] · 13H 2 O (aep = 1‐(2‐amino‐ethyl)‐piperazine) and (H 2 pip) 4 (Hpip) 4 [V 14 Ge 8 O 50 (H 2 O)] (pip = piperazine),45 (dienH 3 ) 4 [V 14 Ge 8 O 42 S 8 ] · 5H 2 O (dien = diethylenetriamine), (aepH 3 ) 4 [V 14 Ge 8 O 42 S 8 ],46 as well as some vanadates with copper amino complexes bound to the central structural vanadate motifs 47,48. All these compounds were synthesized under solvothermal conditions applying NH 4 VO 3 as vanadium source, and the amines used in the syntheses act as reducing agents.…”

New Water‐Soluble Cluster Compound {Zn(en)3}3[V15Sb6O42(H2O)]⋅ (Ethylenediamine)3⋅10 H2O as a Synthon for the Generation of Two New Antimonato Polyoxovanadates

“…The structures of II-IV fea-ture the {V 15 Sb 6 O 42 }c luster (approximate D 3 symmetry; Figure 3) consistingo f1 5e dge-and corner-sharing VO 5 square pyramids and three Sb 2 O 5 handle-like units, whicha re constructed by corner-sharingo ft wo SbO 3 trigonal pyramids with one water molecule in the middle of the cluster shell. [8,13,17,25] In ar ecent DFT-based investigation,w e demonstrated that such SbÀNd istances must be treated as chemicalbonds. The two hexagons are C 4 -symmetrically connected by three VO 5 pyramids (Figure 3l eft, blue pyramids).T he geometric parameters are in full agreement with data reportedi nt he literaturef or {V 15 }-core-containing Sb-POVs (Tables S2-S6).…”

Lithium Argyrodites with Phosphorus and Arsenic: Order and Disorder of Lithium Atoms, Crystal Chemistry, and Phase Transitions

“…During our research in the area of poloxovanadates we successfully synthesized several new chemically modified high nuclearity POVs. like (C 6 H 17 N 3 )[V 16 Sb 4 O 42 ] · 2H 2 O, (NH 4 ) 4 [V 14 Sb 8 O 42 ] · 2H 2 O,33 (trenH 3 ) 2 [V 15 Sb 6 O 42 ] · n H 2 O (tren = tris(2‐aminoethyl)amine),34 [V 16 Sb 4 O 42 (H 2 O){VO(C 6 H 14 N 3 ) 2 } 4 ] · 10H 2 O · C 6 H 14 N 2 35(C 6 H 14 N 2 = (±)‐trans‐1,2‐diaminocyclohexane), [V 14 Sb 8 (C 6 H 15 N 3 ) 4 O 42 (H 2 O)] · 4H 2 O, (C 6 H 17 N 3 ) 2 [V 15 Sb 6 (C 6 H 15 N 3 ) 2 O 42 (H 2 O)] · 2.5H 2 O,36 {[Cu(H 2 O)(C 5 H 14 N 2 ) 2 ] 2 [V 16 O 38 (Cl)]} · 4(C 5 H 15 N 2 ),37 (dien‐H 3 ) 4 [V 14 Ge 8 O 42 S 8 ] · 5H 2 O, (aep‐H 3 ) 4 [V 14 Ge 8 O 42 S 8 ],38 (aepH 3 ) 4 [V 14 Ge 8 O 50 ] · 2(aep) · 13H 2 O (aep = 1‐(2‐amino‐ethyl)‐piperazine) and (pipH 2 ) 4 (Hpip) 4 [V 14 Ge 8 O 50 (H 2 O)] (pip = piperazine)39 under solvothermal conditions. We want to note that polyoxovanadates can also be synthesized under less drastic conditions.…”