Organic Functionalization of Polyoxovanadates: SbN Bonds and Charge Control

Abstract

New docking sites: SbN bonds formed under hydrothermal conditions enable the attachment of primary and secondary organic amines (see structures, C gray, N blue) to antimonato polyoxovanadate cluster anions (polyhedral representations; O red, Sb yellow), whose charge can be compensated by protonated amines.

Unprecedented Connection Mode of [V16Sb4O42(H2O)]8– Cluster Anions by Mn2+ Centered Complexes: Solvothermal Synthesis and Properties of {[Mn(teta)]4V16Sb4O42(H2O}n·[(H2O)12]n

“…All geometric parameters are in the range reported for POVs. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][25][26][27][28][29][30][31][32][33][34][35] (Tables S2 and S3). There are only two structures reported in the CCDC, in which a Mn 2+ cation is coordinated by one teta ligand and two O atoms.…”

“…[1] Since the discovery of the first hetero-POV [V 15 As 6 O 42 (H 2 O)] 6-, [2,3] which is structurally related to the V 18 O 42 cluster by replacing three VO 5 square pyramids by three handle-like As 2 O 5 moieties, many efforts were undertaken preparing new hetero-POVs displaying different chemical compositions and physical properties. Antimony-POVs (Sb-POVs) are a sub-class of the hetero-POVs, of which three cluster types are known: [V 14 16 }.…”

“…[8] While in this compound the {V 16 Sb 4 } core is expanded by a central V IV atom, the application of other transition metal cations in the reaction slurries generated a variety of Sb-POVs with variable dimensionalities. [9][10][11][12][13][14][15][16][17] The chemistry and structural diversity could be expanded by formation of inorganic-organic hybrid structures like observed in [V 14 [18] or in [{Co II (teta) 2 [19] While all these compounds were synthesized under solvothermal conditions applying Sb and V compounds as starting materials, further Sb-POVs could be prepared recently applying a water soluble Sb-POV. [20][21][22] In literature 34 Sb-POVs have been reported, of which 11 belong to the {V 14 16 } cluster is interconnected by a transition metal complex to form a chain, [9] while in all other {V 16 } anion based compounds cations and anions are isolated.…”

A Keggin‐Type Structure Expanded by an Eight‐Membered Ring of Alternating Edge‐Sharing VO5 and VO6 Polyhedra: Solvothermal Synthesis, Crystal Structure, and Magnetic Properties

“…The structural motif of an eight-membered ring is not very common and resembles the eight-membered ring of edge-sharing VO 5 4-cluster. [12][13][14][15][16][17] According to the structure refinement, the eight MO 6 octahedra of the central structural fragment are occupied by both V and W centers in a 1:1 ratio, while the VO 5 pyramids, VO 6 octahedra of the ring, and the central VO 4 …”

“…We note that polyoxidometalates with two encapsulated VO 4 tetrahedra are also known, like e.g. [H 2 V 3 M 17 O 62 ]…”