In situ ligand exchange-mediated 0D/1D transformation of a polyoxovanadate

Abstract

The antimonato-polyoxovanadate {Ni(en)}[VSbO(HO)]·ca.15HO was utilized as a synthon for the solvothermal in situ generation of the new compound {Ni(phen)}[{Ni(en)}VSbO(HO)]·19HO, a rearrangement induced by ligand metathesis. While in the precursor structure cations and anions are isolated, the solid-state structure of the product is characterized by 1D chains consisting of alternating [VSbO(HO)] cluster shells and [Ni(en)] units covalently linked to neighboring clusters via terminal oxygen atoms. Water clusters composed of sixteen hydrogen-bonded HO molecules are located in void spaces of the structure. The magnetic properties indicate weak antiferromagnetic interactions of the bridging Ni center and adjacent polyoxovanadate anions, as well as small magnetic anisotropy of the individual Ni centers.

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

“…[33][34][35] In the structure of III,{ V 15 }c lusters are connected to their nearest neighbors by a[ Zn(en) 2 ] 2 + complex throughO term ÀZnÀ O term interactions to form ac hain directed along [101] ( Figure 6). [23,[36][37][38][39][40][41] The second unique Zn 2 + cation is in a distortedo ctahedral environment made up of three bidentate phen ligands (Tables S3, S5, and S6). The coordination environment is completed by bonds to terminal Oa toms of adjacent clustera nions( ZnÀO: 2.241(4) ), thus leading to ad istorted octahedral [Zn(en) 2 O 2 ] complex( Ta bles S3, S5, and S6).…”

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.…”

Soluble Hetero‐Polyoxovanadates and Their Solution Chemistry Analyzed by Electrospray Ionization Mass Spectrometry

“…We found by time‐dependent ESI‐MS experiments that the Zn‐{V 15 Sb 6 } compound 12 exhibits very similar properties in solution as the earlier investigated Ni‐{V 15 Sb 6 } compound 10 , with the main difference being the significantly prolonged reaction time under ambient conditions for the {V 15 Sb 6 O 42 }→{V 14 Sb 8 O 42 } transformation with 330 hours compared to, respectively, 110 hours after which 50 % conversion is reached. This enabled the rational and selective formation of compounds, which all feature an intact and unchanged {V 15 Sb 6 O 42 } cluster core . Furthermore, the rate of the {V 15 Sb 6 O 42 }→ {V 14 Sb 8 O 42 } cluster transformation significantly increases for both compounds in the same manner, when ammonium acetate was added to the solution, with a time of 23 hours after which 50 % conversion was reached.…”

“…The insights gained when studying the reactivity of the {V 15 Sb 6 O 42 } cluster in compound 10 have proven to be highly valuable for the further development of Sb‐POV chemistry. The versatility of this high‐nuclearity precursor was demonstrated in a number of post‐functionalization reactions, thereby broadening the field of new Sb‐POVs (Scheme ) . The use of this new precursor has enabled the increase in structural complexity of the obtained cluster products, which have partially undergone the {V 15 Sb 6 O 42 }→{V 14 Sb 8 O 42 } transformation after short reaction times.…”

“…Different configurational isomers of the {V 14 Sb 8 O 42 } cluster ( α ‐{Ni(phen) 3 } 2 [V 14 Sb 8 O 42 ]⋅12 H 2 O and β ‐[{Ni(en) 2 } 2 V 14 Sb 8 O 42 ]⋅5.5 H 2 O) were obtained under mild conditions as compared to regular solvothermal syntheses. In addition, it was also possible to prepare a post‐functionalized compound, namely {Ni(phen) 3 } 3 [{Ni(en) 2 }V 15 Sb 6 O 42 ]⋅19 H 2 O, with an unchanged cluster core from compound 10 within 24 hours reaction time …”