Two unusual nanosized Nd3+-substituted selenotungstate aggregates simultaneously comprising lacunary Keggin and Dawson polyoxotungstate segments

Abstract

Two unique nanosized Nd³⁺-substituted selenotungstates Na₉K₈{[W₃Nd₂(H₂O)₃(NO₃)O₆](B-α-SeW₉O₃₃)₂(α-Se₂W₁₄O₅₂)}·35H₂O (1) and [H₂N(CH₃)₂]₇H₉Na₄{[W₂Nd₂(H₂O)₈O₆(OH)₂(β-Se₂W₁₄O₅₂)][W₃Nd₂(H₂O)₆O₇(B-α-SeW₉O₃₃)₂]₂}·84H₂O (2) were prepared by reacting NaSeO₃, Na₂WO₄·2H₂O with Nd(NO₃)₃·6H₂O in aqueous solution by controlling different cations and pH values. 1 was synthesized at pH = 4.3 in the presence of KCl, whereas 2 was synthesized at pH = 3.0 in the presence of [H₂N(CH₃)₂]·Cl. The most striking structural feature of 1 and 2 is the coexistence of vacant Keggin and Dawson segments in the polyoxoanion, which is extremely rare in the field of polyoxometalate chemistry. The trimeric polyoxoanion of 1 can be perceived as a fusion of one α-type tetravacant Dawson [α-Se₂W₁₄O₅₂]¹⁴⁻ unit and two trivacant Keggin [B-α-SeW₉O₃₃]⁸⁻ segments sealing a trigonal bipyramid pentanuclear [W₃Nd₂(H₂O)₃(NO₃)O₆]¹¹⁺ cluster, while the pentameric polyoxoanion of 2 can be described as one β-type tetravacant Dawson [β-Se₂W₁₄O₅₂]¹⁴⁻ fragment and four trivacant Keggin [B-α-SeW₉O₃₃]⁸⁻ segments anchoring a saddle-shaped [W₈Nd₆(H₂O)₂₀O₂₀(OH)₂]²⁴⁺ cluster. In addition, the measurements of catalytic oxidation of aromatic thioethers show that 2 as a catalyst possesses extremely outstanding catalytic performance under mild reaction conditions.