pH-Dependent Assembly of Two Novel Organic–inorganic Hybrids Based on Vanadoantimonate Clusters

Covalent Co–O–V and Sb–N Bonds Enable Polyoxovanadate Charge Control

“…7 There are two examples for the functionalization of Sb-POVs with organic molecules, 8 with the anions [V IV 14 Sb 8 O 42 (H 2 O)] 4– and [V IV 15 Sb 6 O 42 (H 2 O)] 6– displaying covalent bonds to the ammonium cations (C 6 H 15 N 3 ) + with Sb–N bonds from 2.502 to 2.542 Å. Further chemical modification by Zn 2+ -centered complexes was also achieved, 9 leading to 1D chains formed by alternating complexes and polyoxoanions. A [V IV 16 Sb 4 O 42 (H 2 O)] 8– anion with reduced symmetry of the {V 16 } skeleton from D 2 h to C 2 was reported recently.…”

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.…”

“…[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.…”

Configurational Isomerism in Polyoxovanadates

“…50 and 12 kJ mol À1 higher in energy than the previously isolated a and b isomers,respectively.W ed iscuss this unexpected reaction in light of supramolecular SbÀO···V and SbÀO···Sb contacts manifested in {V 14 Sb 8 O 42 } 2 dimers detected in the solid state. This isomer is characterized by the inverted orientation (that is,pointing inwards) of one of its edge-sharing VO 5 pyramids,reducing the molecular symmetry to C 2v .Compound 2 features the first hetero-POV displaying configurational isomerism, and as the isomerization of the vanadyl moieties can occur at different positions, this Sb-POVisfurthermore subject to positional isomerism, [6] an aspect that may complicate synthesis and isolation of atargeted isomer.Thestructures of all hitherto known Sb-POVcluster shells can be derived from the {V IV 18 O 42 }a rchetype by substitution of 2, 3, or 4{ VO 5 }s quare pyramids with dumbbell-like {Sb III 2 O 5 }u nits.O fa ll possible [V 14 Sb 8 O 42 (H 2 O)] 4À isomers (see Supporting Information, Figure S1), the D 2d -symmetric a [7] and the D 2h -symmetric b [8][9][10][11][12][13] isomers have so far been observed. [2] As such, the syntheses of semimetalfunctionalized POVs often are entirely serendipitous.M oreover, within the most widely explored class of antimonato polyoxovanadates, [3] the obtained cluster compounds usually are nearly insoluble,l imiting the study of consecutive reactions.V ery recently,w ed iscovered aw ater-soluble antimonato polyoxovanadate (Sb-POV), {Ni-(en) 3 } 3 [V IV 15 Sb III 6 O 42 (H 2 O) x ]·ca.15 H 2 O( 1; x = 0, 1; en = ethylenediamine), representing as uitable starting material for the in situ generation of novel Sb-POVc ompounds.…”