Classical/Non‐classical Polyoxometalate Hybrids

Abstract

Two polyanions [SeI V 2PdII 4WVI 14O56H]11− and [SeI V 4PdII 4WVI 28O108H12]12− are the first hybrid polyoxometalates in which classical (Group 5/6 metal based) and non‐classical (late transition‐metal based) polyoxometalate units are joined. Requiring no supporting groups, this co‐condensation of polyoxotungstate and isopolyoxopalladate constituents also provides a logical link between POM‐PdII coordination complexes and the young subclass of polyoxopalladates. Solid‐state, solution, and gas‐phase studies suggest interesting specific reactivities for these hybrids and point to several potential derivatives and functionalization strategies.

pH-Controlled One Pot Syntheses of Giant Mo2O2S2-Containing Seleno-Tungstate Architectures

“…The anion has six {Mo 2 O 2 (μ-S) 2 (H 2 O) 2 } 2+ bridges connecting three tetravacant {γ-Se 2 W 14 O 52 } units, which are derivatives of the Dawson-like parent [Se 2 W 18 O 62 ] 8– . These {Se 2 W 14 } units correspond to the γ isomer and differ from the {α-Se 2 W 14 } units reported by Izarova and Kögerler and by Yan and Su or from the {α- P 2 W 14 O 54 } 14– unit reported by Gouzerh et al in 2005 . This {γ-Se 2 W 14 O 52 } tetravacant Dawson structure is relatively rare and was, to our knowledge, only reported by Cronin and co-workers in 2014 as a building unit of the compound [H 12 Pd 10 Se 10 W 52 O 206 ] 28– .…”

Syntheses, Molecular Structures, and Countercation‐Induced Structural Transformation of Monomeric α‐Keggin‐Type Polyoxotungstate‐Coordinated Mono‐ and Dipalladium(II) Complexes

“…[1,2] Various palladium-containing POMs have been reported; [2] however, only in few cases their structure was determined by X-ray crystallography structural analysis. Some recent examples include [Se IV 2 Pd II 4 W VI 14 O 56 H] 11À , [3] [Se IV , [3] [Pd II 4 (α-P 2 W 15 O 56 ) 2 ] 16À , [4] [Pd II 3 (TeW 9 O 33 ) 2 ] 10À , [5] [γ-H 2 SiW 10 O 36 Pd II 2 (OAc) 2 ] 4À , [6] and [{(γ-H 2 SiW 10 O 36 Pd II 2 )(O 2 C-(CH 2 ) n CO 2 )}] (n = 1,3, and 5). [7] In this study, we successfully obtained the cesium and tetramethylammonium salts Cs 5 [α-PW 11 -2).…”

Self-Assembly of Nanoscale Lanthanoid-Containing Selenotungstates: Synthesis, Structures, and Magnetic Studies

“…In the past decades, a combinational strategy for the synthesis of Ln-functionalized nanoscale POM clusters is to take advantage of the Ln cations and various POM BBs possessing strong reactivity on its lacunary sites; on this level, more accessible and metastable BBs formed in situ from preformed POM clusters may bring more diversity to this system. The cyclic {Se 6 W 39 } precursor consisting of {Se 2 W 12 O 46 } units possesses poor aqueous solution stability, and it may in situ decompose into smaller and metastable Se-templated fragments; these BB sources are hard to obtain from a simple Se raw material and possess quite rare and highly reactive toward cationic metal groups, and this process has been well presented in Fe- or Pd-containing selenotungstates. , Thus, 1 – 5 were prepared by the acidification of Gd, Tb, or Dy ions with this {Se 6 W 39 } precursor in the presence of organic amine cations (Figure S1). No products were obtained when simple Se and W salts (Se/W molar ratio ≈ 1:6 as in {Se 6 W 39 }) as starting materials instead of {Se 6 W 39 }; therefore, we primarily confirm that such a preformed precursor brings the necessary BBs with high reactivities to this system.…”