Unraveling the Effects of Cobalt on Crystal Growth and Solution Behavior of Nb₆P₂W₁₂-based Dimeric Clusters

Abstract

We report the synthesis, characterization, and solution self-assembly of plenary Nb6P2W12-based transition-metal substituted polyoxometalate, which is obtained by simply adding transition metals (Co2+) into aqueous solution containing cluster [(NbO2)6P2W12O56]12–, which is obtained by an in situ synthetic method. The incorporation of Co2+ ions significantly affects the crystal structure, resulting in the formation of a 1D chain-like crystal and the first example of a niobotungstate-based cobalt derivative cluster. The behavior and stability of this cluster in solution are confirmed by time-resolved static light scattering, dynamic light scattering, small-angle X-ray scattering, and electrospray mass spectrometry studies.

Cation‐Controlled Assembly of Polyoxotungstate‐Based Coordination Networks

“…All‐inorganic POM coordination networks, such as those shown in Figure , contain POM clusters connected solely through coordinative O–M–O (where M is generally a transition or lanthanide metal) bonds to form one‐dimensional chains, two‐dimensional sheets or three‐dimensionally connected extended solids . Such materials combine the all‐inorganic nature of zeolites with the coordination linkages of MOFs and thus represent an exciting class of materials for realizing and understanding design principles of tunable, molecule‐based metal oxides.…”

Recent studies on the reaction of [X6O19]8− (X = Nb, Ta) polyanions under acidic conditions

“…Another example includes [H 5 (Nb 6 P 2 W 12 ) 2 Co 3 (H 2 O) 11 O 121 ] 7− (Fig. 8f ), 69 which can be viewed as two reversed {Nb 6 P 2 W 12 Co 2 O 68.5 } units interconnected through three Nb-O-Nb bridges. These units subsequently form a one-dimensional (1D) chain through Co ions.…”

Insights into the self-assembly of giant polyoxomolybdates from building blocks to supramolecular structures

“…Electrospray ionization mass spectrometry (ESI-MS) has been employed as a valuable tool to investigate the selfassembly process of Keggin or smaller clusters. [50][51][52][53][54][55][56][57][58][59] However, it is difficult to isolate the information of clusters with the same m/z when applied to giant polyoxomolybdates, because they always have a huge molecular weight and high negative charge. Coupling the means of separation and MS will be an ideal solution.…”