Self-assembly of polyoxoselenitopalladate nanostars [Pd15(μ3-SeO3)10(μ3-O)10Na]9− and their supramolecular pairing in the solid state

Abstract

An anionic Pd₁₅-oxo-cluster [Pd₁₅(μ₃-SeO₃)₁₀(μ₃-O)₁₀Na]⁹⁻ has been synthesized. It is the result of an unprecedented self-assembly of Pd(2+) and Na(+) cations, SeO₃²⁻ and oxo anions. It has been found for the first time, that selenito groups can give rise to supramolecular interactions in the solid state with palladium atoms, through the selenium electron lone pairs.

Noble Metals in Polyoxometalates

“…[153] The solution stability of the star-shaped polyanion has been confirmed by 31 P NMR spectroscopy [151,153] and mass spectrometry. [149,152,153] Although a conventional vanadopalladate is known (Figure 3 a), [9] + (x = 0-2) involving a relatively dense, positively charged shell of countercations surrounding the negatively charged polyanion bowl. The formation and exact composition of such assemblies were confirmed by ESI-MS measurements.…”

“…[148,149] Reaction [147] ering the internuclear separation of 7.4 between the two Cu II ions. [150] The 2 and Na 2 SeO 3 in CH 3 CN/H 2 O (5:1) followed by recrystallization of its sodium salt from water [152] or by direct self-assembly of Pd(CH 3 COO) 2 with SeO 2 in sodium acetate buffer. [145,149] Cronin .…”

Self-assembly and structural transformations of high-nuclearity palladium-rich polyoxometalates

“…2 Comparison of the selenopalladate structural units common to both compounds 1 and 2 and the polyoxopalladate 'cages' and 'nanostars' of the general formulae shown. 13f,g, 16 The supporting POM framework/surrounding oxopalladate cluster associated with each {Pd 5 Se 2 } unit is shown in wireframe, providing an idea of the local environment of each unit. In the case of the polyoxopalladate clusters, it can clearly be seen how the {Pd 5 Se 2 } moiety can be considered as a repeating structural unit in which either; (b) four or (c) five selenopalladate groups are fused to form the overall structure in which the central Pd II ion defines the four-or five-fold symmetry axes of the respective polyoxopalladate clusters.…”

Synthesis, Structural Characterization, and Magnetic Properties of the Heteroleptic Dinuclear Nickel Selenite Complex [{Ni(TMEDA)SeO3}2]

“…All other instrumental parameters were automatically tuned in order to achieve the best ion transmission to the analyzer. 6 as experimentally derived from the X-ray geometry. The water molecules that interact via hydrogen bonding with the selenite anion were included in the calculation to investigate their influence on the exchange coupling constant.…”

“…[16] In addition, a small amount of insoluble NiSeO 3 was also formed, which was filtered off and identified by infrared spectroscopy. [5][6][7][8] Crystals of complex 2 suitable for X-ray diffraction analysis were obtained by slow concentration of the mother liquor at room temperature.…”