High Nuclearity Antimonato‐Polyoxovanadate Cluster {V₁₅Sb₆O₄₂} as a Synthon for the Solvothermal in situ Generation of α‐ and β‐{V₁₄Sb₈O₄₂} Isomers

Abstract

New heteroatom polyoxovanadates (POVs) were synthesized by applying a water-soluble high-nuclearity cluster as new synthon. The [V15 Sb6 O42 ](6-) cluster shell exhibiting D3 symmetry was in situ transformed into completely different cluster shells, namely, the α-[V14 Sb8 O42 ](4-) isomer with D2d and the β-[V14 Sb8 O42 ](4-) isomer with D2h symmetry. The solvothermal reaction of {Ni(en)3 }3 [V15 Sb6 O42 (H2 O)x ]⋅15 H2 O (x=0 or 1; en=ethylenediamine) in water led to the crystallization of [{Ni(en)2 }2 V14 Sb8 O42 ]⋅5.5 H2 O containing the β-isomer. The addition of [Ni(phen)3 ](ClO4 )2 ⋅0.5 H2 O (phen=1,10-phenanthroline) to the reaction slurry gave the new compound {Ni(phen)3 }2 [V14 Sb8 O42 ]⋅phen⋅12 H2 O with the α-isomer. Both transformation reactions are complex due the change of symmetry, the chemical composition, and rearrangement of the VO5 square pyramids and Sb2 O5 handle-like moieties.

Nucleation and Crystal Growth of a {V14Sb8O42} Cluster from a {V15Sb6O42} Polyoxovanadate: In Situ XRD Studies

“…The transformation of a {V 15 Sb 6 O 42 } cluster into a {V 14 Sb 8 O 42 } cluster proceeds by several structural and chemical changes . The {V 15 Sb 6 O 42 } cluster with D 3 symmetry contains 15 edge‐sharing square‐pyramidal VO 5 moieties.…”

“…Hence, the reaction time must be significantly reduced. In the past, we demonstrated for several solvothermal systems that the reaction time can be drastically reduced by stirring the mixture , . During experiments in the laboratory the shortest reaction times were identified for the reaction of compound I (0.045 mmol) with NH 4 VO 3 (0.125 mmol) in a glass tube (inner volume 11 mL) and distilled water (4 mL).…”

“…The addition of [Ni(phen) 3 ](ClO 4 ) 2 · 0.5H 2 O (phen = 1,10‐phenanthroline) to an aqueous solution of I resulted in the crystallization of {Ni(phen) 3 } 2 [V 14 Sb 8 O 42 ] · phen · 12H 2 O ( III ) containing α‐{V 14 Sb 8 O 42 } . Performing the reaction in the presence of Sb 2 O 3 reduced the reaction time to 1 d. On the basis of the observation that the {V 14 Sb 8 O 42 } cluster can be obtained with Sb 2 O 3 in short reaction times, we performed syntheses with NH 4 VO 3 with the aim of preparing the V‐richest cluster {V 16 Sb 4 O 42 }.…”

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

“…[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

“…[4,5] The addition of cyclen (1,4,7,10- 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. [4,5] The addition of cyclen (1,4,7,10- 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.…”