Synthesis, Structure, and Characterization of In10-Containing Open-Wells–Dawson Polyoxometalate

Polyoxometalate-Complexed Indium Hydroxide: Atomically Homogeneous Impregnation via Countercation Exchange

“…Nevertheless, in a previous study, analysis of the vibrational spectra suggested that [α-PW 11 O 39 ]­Fe III O – ligands are bound via μ-O linkages to Fe atoms at the surfaces of α-Fe 2 O 3 NCs. In the present case, it is plausible that the [α 2 -P 2 W 17 O 61 ]­In III OH – ligands are bound via μ-OH linkages to In III atoms at the In­(OH) 3 NC surface, similar to linkages between In III ions in molecular complexes . While this could not be definitively determined from the FTIR and related Raman data (Figure S12), it is, nevertheless, consistent with the remarkably close match between the FTIR spectra of [α 2 -P 2 W 17 O 61 In III OH] 8– and 1 , as shown in the green and black plots, respectively, in Figure a.…”

“…In those complexes, Ti IV or Fe III ions�coordinated in a pentadentate "in-pocket" fashion by monovacant Keggin and Wells−Dawson (WD) anions�form hydrolytically stable μ-O linkages to metal atoms at the surfaces of the respective metal oxide NCs. 12, 13 Importantly, POM-complexed Ti IV and Fe III OH) 13 (H 2 O) 8 )] 17− , 21 suggested that POM-complexed metal ions might form stable μ-OH linkages to metal hydroxide NCs. We now report that In III -substituted monodefect WD cluster anions, [{α 2 -P 2 W 17 O 61 In III OH)] 8− , serve as ligands for stable, water-soluble complexes of predominantly cubic-phase (dzhalindite) In(OH) 3 NCs (1).…”

“…To achieve this, we built upon our use of polyoxometalate (POM) cluster anions as ligands for soluble complexes of anatase-TiO 2 and α-Fe 2 O 3 (hematite) , NCs. In those complexes, Ti IV or Fe III ionscoordinated in a pentadentate “in-pocket” fashion by monovacant Keggin and Wells–Dawson (WD) anionsform hydrolytically stable μ-O linkages to metal atoms at the surfaces of the respective metal oxide NCs. , Importantly, POM-complexed Ti IV and Fe III ions form related oxo linkages in molecular μ-oxo-bridged dimers such as [{PW 11 O 39 Ti} 2 -μ-O] 8– and [{PW 11 O 39 Fe} 2 -μ-O] 10– . , By analogy, the presence of μ-OH linkages between early- and late-transition-metal cations in dimeric POM complexes such as [{PW 11 O 39 Zr} 2 (μ-OH) 2 ] 8– , , [{A-α-PW 9 O 34 } 2 Hf 3 (μ-OH) 3 ] 8– , [{A-α-SiW 9 O 33 } 2 (Fe 4 (OH) 6 )] 10– , and [{A-α-SiW 9 O 33 } 2 (Cu 5 (OH) 4 (H 2 O) 2 ] 10– and between main-group cations in [{α,α-Si 2 W 18 O 66 }­(M 4 (μ-OH) 6 )], where M = Al and Ga, and [(KIn 2 (μ-OH) 2 )­{(α,α-Si 2 W 18 O 66 ) 2 }­(In 6 (μ-OH) 13 (H 2 O) 8 )] 17– , suggested that POM-complexed metal ions might form stable μ-OH linkages to metal hydroxide NCs.…”