Ionothermal synthesis was applied to the formation of polyoxometalates (POMs) and two new compounds [EMIM](8)Na(9)[WFe(9)(micro(3)-O)(3)(micro(2)-OH)(6)O(4)H(2)O(SiW(9)O(34))(3)].7H(2)O (, [EMIM](8)Na(9)[].7H(2)O, EMIM = 1-ethyl-3-methylimidazolium) and [EMIM](4)[SiMo(12)O(40)].12H(2)O (), have been successfully produced in the ionic liquid (IL) [EMIM](4)Br. They were characterized by single-cr...

Caps in α-Keggin-type polyoxometalates [PM2Nb12O40](9-) (M: Nb[double bond, length as m-dash]O or V[double bond, length as m-dash]O) can be removed in basic condition to produce uncapped [PNb12O40](15-). Transmetalation or capping occurs from the reaction of [PNb14O42](9-) or [PNb12O40](15-) with either Sb2O3 or V2O5 to form [PSb2Nb12O40](9-) or [PV2Nb12O42](9-), respectively.

Using carbon monoxide as a probe molecule for the oxidation state of Cu ions, we demonstrated that anchored polynuclear charge-transfer complexes consisting of Ce(III) ions and Cu(II)-substituted Keggin-type polyoxotungstates function as efficient visible-light-driven multielectron-transfer catalysts.

A novel (3,4)-connected 3D self-penetrating metal-organic framework with a nanometre-scale cavity constructed from metallacalix[4]arene building blocks and Keggin-type polyanions has been obtained by using a 1,3-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)propane ligand.

The rational self-assembly of mono-lacunary Keggin clusters with 4d and 4f metal salts via a conventional method has yielded two novel polyoxometalate-based 4d–4f heterometallic compounds containing lacunary Keggin anions connected to ten metal atoms: {[Ag{Ag2(H2O)4}{Ln(H2O)6}2H ⊂ {SiW11Ln(H2O)4O39}2]·nH2O (Ln = Ce and n = 7 for 1, Ln = Pr and n = 3 for 2). Their structures were determined by s...

A Keggin-type arsenotungstate anion-supported iron-bipyridine complex, [Fe(2,2′-bipy)3]1.5[AsWVI10WV2O40Fe(2,2′-bipy)2(H2O)] · 0.25H2O, has been hydrothermally synthesized and characterized by IR and ESR spectra, TG-DTA analysis, and single crystal X-ray diffraction. Each structural unit of the title compound consists of one [AsWVI10WV2O40Fe(2,2′-bipy)2(H2O)]3− heteropolyanion, one and a half [...

The chemistry of polyoxoanions has been studied extensively.1-12 A large body of experimental knowledge has been accumulated on these oxide clusters, which can in many instances be reduced, maintaining their integrity with only subtle changes in their structure.7a,12 Trends in the obtention of blue reduced species have been empirically established over time, and the nature of electronic delocal...

Immobilization of the chiral salen-metal complex [Mn(III)(salen)(H(2)O)(2)ClO(4)] on the Keggin-type polyoxometalate (POM) skeletons leads to the isolation of POM derivatives functionalized with chiral salen-metal complexes, which represent the first examples of introducing chiral salen-metal complexes into the POM systems.

The reaction of a saddle-distorted Mo(v)-dodecaphenylporphyrin complex and a Keggin-type polyoxometalate gives a discrete and nanosized molecule, [{Mo(DPP)(O)}(2)(H(2)SiW(12)O(40))], which involves direct coordination between the Mo(v) centers and terminal oxo groups of the polyoxometalate and exhibits excellent stability in solution to show reversible multi-redox processes.