Post transition metal substituted Keggin-type POMs as thin film chemiresistive sensors for H2O and CO2 detection.

Chemiresitive sensing allows the affordable and facile detection of small molecules such as H2O and CO2. Herein, we report a novel class of Earth-abundant post transition metal substituted Keggin polyoxometalates (POMs) for chemiresistive sensing applications, with conductivities up to 0.01 S cm-1 under 100% CO2 and 65% Relative Humidity (RH).

A thirty-year old mystery solved: identification of a new heptatungstate from non-aqueous solutions.

A new isopolyoxotungstate has been characterised, thirty years since the first spectroscopic evidence of its existence. The heptatungstate [W7O24H]5-, containing a {W5} lacunary Lindqvist unit fused to a ditungstate fragment, has significant stability and is only the third isopolytungstate structure to be obtained from non-aqueous systems.

Ultrahigh Proton Conduction via Extended Hydrogen-Bonding Network in a Preyssler-Type Polyoxometalate-Based Framework Functionalized with a Lanthanide Ion.

The exploration of composition-structure-function relationship in proton-conducting solids remains a challenge in materials chemistry. Polyoxometalate-based compounds have been long considered as candidates for proton conductors; however, their low structural stability and a large decrease in conductivity under reduced relative humidity (RH) have limited their applications. To overcome such limitations, the hybridization of polyoxometalates with proton-conducting polymers has emerged as a promising method. Besides, 4f lanthanide ions possess a high coordination number, which can be utilized to attract water molecules and to build robust frameworks. Herein, a Preyssler-type polyoxometalate functionalized with a 9-coordinate Eu3+ (Eu[P5W30O110K]11-) is newly synthesized and combined with poly(allylamine) with amine moieties as protonation sites. The resulting robust crystalline composite exhibits an ultrahigh proton conductivity >10-2 S cm-1 at 368 K and 90% RH, which is still >10-3 S cm-1 at 50% RH, due to the strengthened and extended hydrogen-bonding network.

Self-assembly of amphiphilic polyoxometalates for the preparation of mesoporous polyoxometalate-titania catalysts.

Amphiphilic polyoxometalate (POM) surfactants were prepared by covalently grafting double hydrophobic tails with chain lengths C12H25, C14H29, C16H33 or C18H37 onto the lacunary Wells-Dawson {P2W17O61} headgroup. The critical micelle concentrations (CMCs) of these novel surfactants in aqueous solutions were determined by conductivity, and micelle formation was studied by small angle neutron scattering (SANS). Surprisingly, the amphiphiles with longer hydrophobic tails tend to form less elongated and more globular micelles in water. The self-assembled amphiphilic polyoxometalates were used as templates in the hydrothermal synthesis of mesoporous TiO2 containing dispersed, immobilised {P2W17O61} units, which showed enhanced activity for the photodegradation of rhodamine B (RhB). The catalyst was recycled eight times with no loss of efficiency, demonstrating the stability of the hybrid structure. The amphiphilic polyoxometalates, therefore have excellent potential for the synthesis of various types of catalytically active porous materials.

Antagonistic mixing in micelles of amphiphilic polyoxometalates and hexaethylene glycol monododecyl ether.

HYPOTHESIS: Polyoxometalates (POMs) are metal oxygen clusters with a range of interesting magnetic and catalytic properties. POMs with attached hydrocarbon chains show amphiphilic behaviour so we hypothesised that mixtures of a nonionic surfactant and anionic surfactants with a polyoxometalate cluster as headgroup would form mixed micelles, giving control of the POM density in the micelle, and which would differ in size and shape from micelles formed by the individual surfactants. Due to the high charge and large size of the POM, we suggested that these would be nonideal mixtures due to the complex interactions between the two types of surfactants. The nonideality and the micellar composition may be quantified using regular solution theory. With supplementary information provided by small-angle neutron scattering (SANS), an understanding of this unusual binary surfactant system can be established. EXPERIMENTS: A systematic study was performed on mixed surfactant systems containing polyoxometalate-headed amphiphiles (K10[P2W17O61OSi2(CnH2n+1)2], abbreviated as P2W17-2Cn, where n = 12, 14 or 16) and hexaethylene glycol monododecyl ether (C12EO6). Critical micelle concentrations (CMCs) of these mixtures were measured and used to calculate the interaction parameters based on regular solution theory, enabling prediction of micellar composition. Predictions were compared to micelle structures obtained from SANS. A phase diagram was also established. FINDINGS: The CMCs of these mixtures suggest unusual unfavourable interactions between the two species, despite formation of mixed micelles. Micellar compositions obtained from SANS concurred with those calculated using the averaged interaction parameters for P2W17-2Cn/C12EO6 (n = 12 and 14). We attribute the unfavourable interactions to a combination of different phenomena: counterion-mediated interactions between P2W17 units and the unfolding of the ethylene oxide headgroups of the nonionic surfactant, yet micelles still form in these systems due to the hydrophobic interactions between surfactant tails.

Bonding Insights from Structural and Spectroscopic Comparisons of {SnW5 } and {TiW5 } Alkoxido- and Aryloxido-Substituted Lindqvist Polyoxometalates.

Incorporation of {MX}n+ groups into polyoxometalates (POMs) provides the means not only to introduce reactivity and functionality but also to tune the electronic properties of the oxide framework by varying M, X and n. In order to elucidate the factors responsible for differences in reactivity between {TiW5 } and {SnW5 } Lindqvist-type hexametalates, a series of alkoxido- and aryloxido-tin substituted POMs (nBu4 N)3 [(RO)SnW5 O18 ] (R=Me, Et, iPr and tBu) and (nBu4 N)3 [(ArO)SnW5 O18 ] (Ar=C6 H5 , 4-MeC6 H5 , 4-tBuC6 H5 , 4-HOC6 H4 , 3-HOC6 H4 and 2-CHOC6 H4 ) has been structurally characterised and studied by multinuclear NMR (1 H, 13 C, 17 O, 119 Sn and 183 W) and FTIR spectroscopy. Spectroscopic and structural parameters were compared with those of titanium-substituted homologues and, when coupled with theoretical studies, indicated that Sn-OR and Sn-OAr bonds are ionic with little π-contribution, whereas Ti-OR and Ti-OAr bonds are more covalent with π-bonding that is more prevalent for Ti-OR than Ti-OAr. This experimental and theoretical analysis of bonding in a homologous series of reactive POMs is the most extensive and detailed to date, and reveals factors which account for significant differences in reactivity between tin and titanium congeners.

Synthesis and characterization of the platinum-substituted Keggin anion α-H2SiPtW11O40(4-).

Acidification of an aqueous solution of K8SiW11O39 and K2Pt(OH)6 to pH 4 followed by addition of excess tetramethylammonium (TMA) chloride yielded a solid mixture of TMA salts of H2SiPtW11O40(4-) (1) and SiW12O40(4-) (2). The former was separated from the latter by extraction into an aqueous solution and converted into tetra-n-butylammonium (TBA) and potassium salts TBA-1 and K-1. The α-H2SiPtW11O40(4-) was identified as a monosubstituted Keggin anion using elemental analysis, IR spectroscopy, X-ray crystallography, electrospray ionization mass spectrometry, (195)Pt NMR spectroscopy, (183)W NMR spectroscopy, and (183)W-(183)W 2D INADEQUATE NMR spectroscopy. Both TBA-1 and K-1 readily cocrystallized with their unsubstituted Keggin anion salts, TBA-2 and K-2, respectively, providing an explanation for the historical difficulty of isolating certain platinum-substituted heteropolyanions in pure form.

A redox-triggered structural rearrangement in an iodate-templated polyoxotungstate cluster cage.

The new tungstatoiodate, α-[H5W18O59(IO3)](6-), containing I(V)O3(-) within a {W18O54} metal oxide framework has been prepared and shown by X-ray crystallography and mass spectrometry to be derived from the fully oxidised [H3W18O56(IO6)](6-) by two-electron reduction accompanied by a redox-triggered structural rearrangement where three I-O covalent bonds are broken.

Rational addition of capping groups to the phosphomolybdate Keggin anion [PMo12O40](3-) by mild, non-aqueous reductive aggregation.

Controlled reductive assembly of capped Keggin anions [PMo(12)O(40)(ML(m))(n)](3-) has been achieved by reduction of [PMo(12)O(40)](3-) with sodium-mercury amalgam in the presence of metal halides, as exemplified by the rational syntheses of mono-capped [PMo(12)O(40){Co(MeCN)(2)}](3-) and bi-capped [PMo(12)O(40)(VO)(2)](3-) and [PMo(12)O(40)Sb(2)](3-).

Protonolysis of [((i)PrO)TiMo5O18]3-: access to a family of TiMo5 Lindqvist type polyoxometalates.

The tetra-n-butylammonium (TBA) salts of [((i)PrO)TiMo(5)O(18)](3-) 1 and [((i)BuO)TiMo(5)O(18)](3-) 2 were prepared by hydrolysis of mixtures of (TBA)(2)[Mo(2)O(7)], (TBA)(4)α-[Mo(8)O(26)] and Ti(OR)(4) (R = (i)Pr or (i)Bu) in acetonitrile. Treatment of (TBA)(3)1 with alcohols ROH afforded primary and tertiary alkoxide derivatives [(RO)TiMo(5)O(18)](3-) (R = Me 3, (t)Bu 4), whilst aryloxides [(ArO)TiMo(5)O(18)](3-) were prepared by reacting 1 with phenols ArOH (Ar = C(6)H(4)Me-4 5, and C(6)H(4)CHO-2 6). Oxo-bridged [(µ-O)(TiMo(5)O(18))(2)](6-)7 rather than the hydroxo derivative [(HO)TiMo(5)O(18)](3-) was obtained upon hydrolysis of 1. X-Ray crystal structures of TBA salts of anions 3-7 show that titanium is six-coordinate in all cases, although titanium sites are disordered over two trans positions in 3. Mo-O bond length alternation is observed in the Mo(4)O(4) planes of 4 and 7 and in one of the two independent anions in the structure of 3. In solution, (17)O NMR spectra are consistent with the higher anionic charge compared to [Mo(6)O(19)](2-) and reveal an order of basicity for the anions [LM'Mo(5)O(18)](3-) associated with the ability of {LM'}(3+) to donate/withdraw electron density from {Mo(5)O(18)}(6-). Protonolysis reactions of 1 and 3 were slower than for tungstate analogues and the possibility of initial protonation at TiOM (M = Mo) rather than TiOR (M = W) in a proton-assisted S(N)1 mechanism for ligand exchange in [(RO)TiM(5)O(18)](3-) is discussed.

Non-aqueous synthetic methodology for TiW(5) polyoxometalates: protonolysis of [(MeO)TiW(5)O(18)](3-) with alcohols, water and phenols.

The tetra-n-butylammonium (TBA) salt of [(MeO)TiW(5)O(18)](3-) 1 was reacted with alcohols ROH to give primary, secondary and tertiary alkoxide derivatives [(RO)TiW(5)O(18)](3-) (R = Et 2, (i)Pr 3 and (t)Bu 4), whilst hydrolysis afforded [(mu-O)(TiW(5)O(18))(2)](6-) 5 rather than the hydroxo derivative (R = H). In reactions with (i)PrOH and (t)BuOH, impurity peaks observed at 1015 and 1020 ppm in the (17)O NMR spectra indicate alkoxide degradation and Ti=O bond formation via reactions analogous to those occurring at the surfaces of solid heteropolyacids. Aryloxides [(ArO)TiW(5)O(18)](3-) were prepared by reacting 1 with phenols ArOH (Ar = C(6)H(5) 6, C(6)H(4)Me-4 7, C(6)H(4)(t)Bu-4 8, C(6)H(4)OH-4 9, C(6)H(4)OH-3 10, C(6)H(3)(OH)(2)-3,5 11 and C(6)H(4)CHO-2 13). TiW(5)O(18) units were linked by reacting 1 with 9 to give [(mu-1,4-OC(6)H(4)O)(TiW(5)O(18))(2)](6-) 12. (17)O and (183)W NMR spectra are reported and X-ray crystal structures were obtained for TBA salts of anions 3-10 and 13, which showed that the titanium is six-coordinate in all cases. Reactions were monitored by (1)H NMR, including a 2D-EXSY study of methoxo exchange, and the slow rates observed are probably associated with the reluctance of titanium in these anions to achieve seven-coordination.

Synthesis and reactivity of the methoxozirconium pentatungstate (nBu4N)6[{(mu-MeO)ZrW5O18}2]: insights into proton-transfer reactions, solution dynamics, and assembly of {ZrW5O18}2- building blocks.

The methoxo-bridged, dimeric, ZrIV-substituted Lindqvist-type polyoxometalate (POM) (nBu4N)6[{(mu-MeO)ZrW5O18}2], (TBA)61, has been synthesized by stoichiometric hydrolysis of Zr(OnPr)4, [{Zr(OiPr)3(mu-OnPr)(iPrOH)}2], or [{Zr(OiPr)4(iPrOH)}2] and [{WO(OMe)4}2] in the presence of (nBu4N)2WO4, providing access to the systematic nonaqueous chemistry of ZrW5 POMs for the first time and an efficient route to 17O-enriched samples for 17O NMR studies. 1H NMR provided no evidence for dissociation of 1 in solution, although exchange with MeOH was shown to be slow by an EXSY study. Reactions with HX at elevated temperatures gave a range of anions [{XZrW5O18}n]3n- (X = OH, 3; OPh, 4; OC6H4Me-4, 5; OC6H4(CHO)-2, 6; acac, 7; OAc, 8), where n = 2 for 3 and n = 1 for 4-8, while 1H and 17O NMR studies of hydrolysis of 1 revealed the formation of an intermediate [(mu-MeO)(mu-HO)(ZrW5O18)2]6-. Electrospray ionization mass spectrometry of 1 and 3 illustrated the robust nature of the ZrW5O18 framework, and X-ray crystal structure determinations showed that steric interactions between ligands X and the ZrW5O18 surface are important. The coordination number of Zr is restricted to six in aryloxides 4 and 5, while seven-coordination is achieved in the chelate complexes 6-8. Given the inert nature of the methoxo bridges in 1, protonation of ZrOW sites is proposed as a possible step in reactions with HX. The diphenylphosphinate ligand in [(Ph2PO2)ZrW5O18]3- was found to be labile and upon attempted recrystallization the aggregate [(mu3-HO)2(ZrW5O18)3H]7- 9 was formed, which was found to be protonated at ZrOZr and ZrOW sites. This work demonstrates the flexibility of the {ZrW5O18}2- core as a molecular platform for modeling catalysis by tungstated zirconia surfaces.

An alkoxide cluster with 18 Li+ ions encapsulating two borate anions, [((t)BuO)12Li18(BO3)2].

The title compound, bis(borato)dodeca(tert-butoxo)octadecalithium, [Li(18)(BO(3))(2)(C(4)H(9)O)(12)], is formulated conveniently as [(((t)BuOLi)(3)(Li(3)BO(3)))(2)((t)BuOLi)(6)]. A central 12-membered ring and two outer six-membered rings are formed by alternating Li(+) cations and alkoxide O atoms. Sandwiched between the central ring and each of the outer rings is a planar array of three further Li(+) cations surrounding a [BO(3)](3-) anion. Thus, the molecule consists of a cationic [Li(18)(O(t)Bu)(12)](6+) cage encapsulating two borate anions. This compound is the first example of a structurally characterized polynuclear lithium borate, and a rare case of a lithium alkoxide cage with nuclearity greater than eight. All the alkoxide ligands are triply bridging, and the lithium ions have trigonal-planar, trigonal-pyramidal and fourfold coordination, all with major distortions from regular coordination geometry.