Four‐Shell Polyoxometalates Featuring High‐Nuclearity Ln26 Clusters: Structural Transformations of Nanoclusters into Frameworks Triggered by Transition‐Metal Ions

A series of polyoxometalates (POMs) that incorporate the highest‐nuclearity Ln clusters that have been observed in such structures to date (Ln₂₆ , Ln=La and Ce) are described, which exhibit giant multishell configurations (Ln⊂W₆⊂Ln₂₆⊂W₁₀₀). Their structures are remarkably different from known giant POMs that feature multiple Ln ions. In particular, the incorporated Ln–O clusters with a nuclearity of 26 are significantly larger than known high‐nuclearity (≤10) Ln–O clusters in POM chemistry. Furthermore, they also contain the largest number of La and Ce centers for any POM reported to date and represent a new kind of rare giant POMs with more than 100 W atoms. Interestingly, the La₂₆‐containing POM can undergo a single‐crystal to single‐crystal structural transformation in the presence of various transition‐metal ions, such as Cu²⁺, Co²⁺, and Ni²⁺, from an inorganic molecular nanocluster into an inorganic–organic hybrid extended framework that is built from POM building blocks with even higher‐nuclearity La₂₈ clusters bridged by transition‐metal complexes.     

Grafting of Secondary Diolamides onto [P2W15V3O62]9− Generates Hybrid Heteropoly Acids

The Dawson tungstovanadate [P₂W₁₅V₃O₆₂]^9? can be grafted to secondary diolamides. The electron‐withdrawing character of the polyanion increases the acidity of the amide proton, leading to an organo‐polyoxometalate, which can be used as a Brønsted organocatalyst. High‐field NMR and DFT modeling indicate that the amide proton stays on the nitrogen and that the exalted acidity derives from the interaction between the organic and inorganic parts of the organo‐polyoxometalate. The amide‐inserted vanadotungstates thus form a new family of (hybrid) heteropolyacids, offering new perspectives for the application of POM‐based catalysis in organic synthesis.     

A Molecular Placeholder Strategy To Access a Family of Transition‐Metal‐Functionalized Vanadium Oxide Clusters

Systematic access to metal‐functionalized polyoxometalates has thus far been limited to lacunary tungsten oxide and molybdenum oxide clusters. The first controlled, stepwise bottom‐up assembly route to metal‐functionalized molecular vanadium oxides is now presented. A di‐vacant vanadate cluster with two metal binding sites, (DMA)₂[V₁₂O₃₂Cl]^3? (DMA=dimethylammonium) is formed spontaneously in solution and characterized by single‐crystal X‐ray diffraction, ESI mass spectrometry, ⁵¹V NMR spectroscopy, and elemental analyses. In the cluster, the metal binding sites are selectively blocked by hydrogen‐bonded DMA placeholder cations. Reaction of the cluster with transition metals TM (Fe³⁺, Co²⁺, Cu²⁺, Zn²⁺) gives access to mono‐functionalized vanadate clusters (DMA)[{TM(L)}V₁₂O₃₂Cl]^n? (L=ligand). Metal binding is accomplished by significant distortions of the vanadium oxide framework reminiscent of a pincer movement. Cluster stability under technologically relevant conditions in the solid‐state and solution is demonstrated.     

Covalent Attachment of Anderson‐Type Polyoxometalates to Single‐Walled Carbon Nanotubes Gives Enhanced Performance Electrodes for Lithium Ion Batteries

Single‐walled carbon nanotubes (SWNTs) covalently functionalized with redox‐active organo‐modified polyoxometalate (POM) clusters have been synthesized and employed as electrode materials in lithium ion batteries. The Anderson cluster [MnMo₆O₂₄]^9? is functionalized with Tris (NH₂C(CH₂OH)₃) moieties, giving the new organic–inorganic hybrid [N(nC₄H₉)₄]₃[MnMo₆O₁₈{(OCH₂)₃CNH₂}₂]. The compound is then covalently attached to carboxylic acid‐functionalized SWNTs by amide bond formation and the stability of this nanocomposite is confirmed by various spectroscopic methods. Electrochemical analyses show that the nanocomposite displays improved performance as an anode material in lithium ion batteries compared with the individual components, that is, SWNTs and/or Anderson clusters. High discharge capacities of up to 932 mAh g^?1 at a current density of 0.5 mA cm^?2 can be observed, together with high long‐term cycling stability and decreased electrochemical impedance. Chemisorption of the POM cluster on the SWNTs is shown to give better electrode performance than the purely physisorbed analogues.     

Pyrene‐Anderson‐Modified CNTs as Anode Materials for Lithium‐Ion Batteries

An organo‐functionalized polyoxometalate (POM)–pyrene hybrid (Py‐Anderson) has been used for noncovalent functionalization of carbon nanotubes (CNTs) to give a Py‐Anderson‐CNT nanocomposite through π–π interactions. The as‐synthesized nanocomposite was used as the anode material for lithium‐ion batteries, and shows higher discharge capacities and better rate capacity and cycling stability than the individual components. When the current density was 0.5 mA cm^?2, the nanocomposite exhibited an initial discharge capacity of 1898.5 mA h g^?1 and a high discharge capacity of 665.3 mA h g^?1 for up to 100 cycles. AC impedance spectroscopy provides insight into the electrochemical properties and the charge‐transfer mechanism of the Py‐Anderson‐CNTs electrode.     

Polyoxometalate Ionic Liquids as Self‐Repairing Acid‐Resistant Corrosion Protection

Corrosion is a global problem for any metallic structure or material. Herein we show how metals can easily be protected against acid corrosion using hydrophobic polyoxometalate‐based ionic liquids (POM‐ILs). Copper metal disks were coated with room‐temperature POM‐ILs composed of transition‐metal functionalized Keggin anions [SiW₁₁O₃₉TM(H₂O)]^n? (TM=Cu^II, Fe^III) and quaternary alkylammonium cations (C_nH_{2 n+1})₄N⁺ (n=7–8). The corrosion resistance against acetic acid vapors and simulated “acid rain” was significantly improved compared with commercial ionic liquids or solid polyoxometalate coatings. Mechanical damage to the POM‐IL coating is self‐repaired in less than one minute with full retention of the acid protection properties. The coating can easily be removed and recovered by rinsing with organic solvents.     

Stabilization of Low‐Valent Iron(I) in a High‐Valent Vanadium(V) Oxide Cluster

Low‐valent iron centers are critical intermediates in chemical and bio‐chemical processes. Herein, we show the first example of a low‐valent Fe^I center stabilized in a high‐valent polyoxometalate framework. Electrochemical studies show that the Fe^III‐functionalized molecular vanadium(V) oxide (DMA)[Fe^IIIClV^V₁₂O₃₂Cl]³⁻ (DMA=dimethylammonium) features two well‐defined, reversible, iron‐based electrochemical reductions which cleanly yield the Fe^I species (DMA)[Fe^IClV^V₁₂O₃₂Cl]⁵⁻. Experimental and theoretical studies including electron paramagnetic resonance spectroscopy and density functional theory computations verify the formation of the Fe^I species. The study presents the first example for the seemingly paradoxical embedding of low‐valent metal species in high‐valent metal oxide anions and opens new avenues for reductive electron transfer catalysis by polyoxometalates.     

Classical/Non‐classical Polyoxometalate Hybrids

Two polyanions [Se^{I V}₂Pd^II₄W^VI₁₄O₅₆H]^11? and [Se^{I V}₄Pd^II₄W^VI₂₈O₁₀₈H₁₂]^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‐Pd^II 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.     

Epoxidation of cyclohexene with H2O2 over efficient water‐tolerant heterogeneous catalysts composed of mono‐substituted phosphotungstic acid on co‐functionalized SBA‐15

A series of Keggin‐type heteropolyacid‐based heterogeneous catalysts (Co‐/Fe‐/Cu‐POM‐octyl‐NH₃‐SBA‐15) were synthesized via immobilized transition metal mono‐ substituted phosphotungstic acids (Co‐/Fe‐/Cu‐POM) on octyl‐amino‐co‐functionalized mesoporous silica SBA‐15 (octyl‐NH₂‐SBA‐15). Characterization results indicated that Co‐/Fe‐/Cu‐POM units were highly dispersed in mesochannels of SBA‐15, and both types of Brønsted and Lewis acid sites existed in Co‐/Fe‐/Cu‐POM‐octyl‐NH₃‐SBA‐15 catalysts. Co‐POM‐octyl‐NH₃‐SBA‐15 catalyst showed excellent catalytic performance in H₂O₂‐mediated cyclohexene epoxidation with 83.8% of cyclohexene conversion, 92.8% of cyclohexene oxide selectivity, and 98/2 of epoxidation/allylic oxidation selectivity. The order of catalytic activity was Co‐POM‐octyl‐NH₃‐SBA‐15 > Fe‐POM‐octyl‐NH₃‐SBA‐15 > Cu‐POM‐octyl‐NH₃‐SBA‐15. In order to obtain insights into the role of ‐octyl moieties during catalysis, an octyl‐free catalyst (Co‐POM‐NH₃‐SBA‐15) was also synthesized. In comparison with Co‐POM‐NH₃‐SBA‐15, Co‐POM‐octyl‐NH₃‐SBA‐15 showed enhanced catalytic properties (viz. activity and selectivity) in cyclohexene epoxidation. Strong chemical bonding between ‐NH₃⁺ anchored on the surface of SBA‐15 and heteropolyanions resulted in excellent stability of Co‐POM‐octyl‐NH₃‐SBA‐15 catalyst, and it could be reused six times without considerable loss of activity.     

Electrografting of Diazonium‐Functionalized Polyoxometalates: Synthesis,Immobilisation and Electron‐Transfer Characterisation from Glassy Carbon

Polyoxometalates (POMs) are attractive candidates for the rational design of multi‐level charge‐storage materials because they display reversible multi‐step reduction processes in a narrow range of potentials. The functionalization of POMs allows for their integration in hybrid complementary metal oxide semiconductor (CMOS)/molecular devices, provided that fine control of their immobilisation on various substrates can be achieved. Owing to the wide applicability of the diazonium route to surface modification, a functionalized Keggin‐type POM [PW₁₁O₃₉{Ge(p‐C₆H₄‐C?C‐C₆H₄‐${{\rm N}{{+\hfill \atop 2\hfill}}}$ )}]^3? bearing a pending diazonium group was prepared and subsequently covalently anchored onto a glassy carbon electrode. Electron transfer with the immobilised POM was thoroughly investigated and compared to that of the free POM in solution.     

Tuning the Photoisomerization of a N^C‐Chelate Organoboron Compound with a Metal?Acetylide Unit

To examine the impact of metal moieties that have different triplet energies on the photoisomerization of B(ppy)Mes₂ compounds (ppy=2‐phenyl pyridine, Mes=mesityl), three metal‐functionalized B(ppy)Mes₂ compounds, Re‐B , Au‐B , and Pt‐B , have been synthesized and fully characterized. The metal moieties in these three compounds are Re(CO)₃(tert‐Bu₂bpy)(C?C), Au(PPh₃)(C?C), and trans‐Pt(PPh₃)₂(C?C)₂, respectively, which are connected to the ppy chelate through the alkyne linker. Our investigation has established that the Re^I unit completely quenches the photoisomerization of the boron unit because of a low‐lying intraligand charge transfer/MLCT triplet state. The Au^I unit, albeit with a triplet energy that is much higher than that of B(ppy)Mes₂, upon conjugation with the ppy chelate unit, substantially increases the contribution of the π→π* transition, localized on the conjugated chelate backbone in the lowest triplet state, thereby leading to a decrease in the photoisomerization quantum efficiency (QE) of the boron chromophore when excited at 365 nm. At higher excitation energies, the photoisomerization QE of Au‐B is comparable to that of the silyl–alkyne‐functionalized B(ppy)Mes₂ ( TIPS‐B ), which was attributable to a triplet‐state‐sensitization effect by the Au^I unit. The Pt^II unit links two B(ppy)Mes₂ together in Pt‐B , thereby extending the π‐conjugation through both chelate backbones and leading to a very low QE of the photoisomerization. In addition, only one boron unit in Pt‐B undergoes photoisomerization. The isomerization of the second boron unit is quenched by an intramolecular energy transfer of the excitation energy to the low‐energy absorption band of the isomerized boron unit. TD‐DFT computations and spectroscopic studies of the three metal‐containing boron compounds confirm that the photoisomerization of the B(ppy)Mes₂ chromophore proceeds through a triplet photoactive state and that metal units with suitable triplet energies can be used to tune this system.     

Synthesis and Disassembly/Reassembly of Giant Ring‐Shaped Polyoxotungstate Oligomers

The disassembly and reassembly of giant molecules are essential processes in controlling the structure and function of biological and artificial systems. In this work, the disassembly and reassembly of a giant ring‐shaped polyoxometalate (POM) without isomerization of the monomeric units is reported. The reaction of a hexavacant lacunary POM that is soluble in organic solvents, [P₂W₁₂O₄₈]^14?, with manganese cations gave the giant ring‐shaped POM [{γ‐P₂W₁₂O₄₈Mn₄(C₅H₇O₂)₂(CH₃CO₂)}₆]^42?. This POM is a hexamer of manganese‐substituted {P₂W₁₂O₄₈Mn₄} units, and its inner cavity was larger than any of those previously reported for ring‐shaped polyoxotungstates. It was disassembled into monomeric units in acetonitrile, and the removal of the capping organic ligands on the manganese cations led to reassembly into a tetrameric ring‐shaped POM, [{γ‐P₂W₁₂O₄₈Mn₄(H₂O)₆}₄(H₂O)₄]^24?.     

Synthesis and Characterization of a Thermoresponsive Polyoxometalate–Polymer Hybrid

We report the synthesis of the first organo‐POM with thermoresponsive properties. Our concept will provide chemists with a new tool to design POMs whose solubility is reversibly controllable through an external stimulus. POM–polymer TBA₇[POM]‐poly(N,N‐diethylacrylamide) (POM–PDEAAm), was prepared by grafting PDEAAm‐NH₂ (obtained by RAFT polymerization) onto the activated Dawson acyl‐POM, α₂‐[P₂W₁₇O₆₁SnCH₂CH₂C(?O)]^6?. Extensive MS analysis was used to monitor the chain‐functionalization steps and to confirm the formation of the hybrid. Aqueous solutions of the (NH₄)₇[POM–PDEAAm] exhibited a LCST of 38 °C. Thus, the solubility/aggregation of the hybrid was reversibly controlled by changing the temperature. Above 38 °C, the solution became cloudy, and cleared again upon cooling. Dynamic light scattering (DLS) revealed the formation of small aggregates in the range 100 nm. We assumed that the charged POM head units prevented the formation of the larger‐scattering aggregates that are usually observed for PDEAAm, and promoted the formation of micelle‐like structures. The conjugate exhibited a temperature transition, which was different from that of the polymer and depended on the counterions associated with the POM. This result demonstrates the potential for merging organic (in this case, polymer) and inorganic structures to afford materials that exhibit new properties.     

The Enhancement on Proton Conductivity of Stable Polyoxometalate‐Based Coordination Polymers by the Synergistic Effect of MultiProton Units

Two novel polyoxometalate (POM)‐based coordination polymers, namely, [Co(bpz)(Hbpz)][Co(SO₄)_0.5(H₂O)₂(bpz)]₄ [PMo^VI₈Mo^V₄V^IV₄O₄₂]?13 H₂O ( NENU‐530 ) and [Ni₂(bpz)(Hbpz)₃(H₂O)₂][PMo^VI₈Mo^V₄V^IV₄O₄₄]?8 H₂O ( NENU‐531 ) (H₂bpz=3,3′,5,5′‐tetramethyl‐4,4′‐bipyrazole), were isolated by hydrothermal methods, which represented 3D networks constructed by POM units, the protonated ligand and sulfate group. In contrast with most POM‐based coordination polymers, these two compounds exhibit exceptional excellent chemical and thermal stability. More importantly, NENU‐530 shows a high proton conductivity of 1.5×10^?3 S cm^?1 at 75 °C and 98 % RH, which is one order of magnitude higher than that of NENU‐531 . Furthermore, structural analysis and functional measurement successfully demonstrated that the introduction of sulfate group is favorable for proton conductivity. Herein, the syntheses, crystal structures, proton conductivity, and the relationship between structure and property are presented.     

Visible‐Light‐Driven Water Oxidation by a Molecular Manganese Vanadium Oxide Cluster

Photosynthetic water oxidation in plants occurs at an inorganic calcium manganese oxo cluster, which is known as the oxygen evolving complex (OEC), in photosystem II. Herein, we report a synthetic OEC model based on a molecular manganese vanadium oxide cluster, [Mn₄V₄O₁₇(OAc)₃]^3?. The compound is based on a [Mn₄O₄]⁶⁺ cubane core, which catalyzes the homogeneous, visible‐light‐driven oxidation of water to molecular oxygen and is stabilized by a tripodal [V₄O₁₃]^6? polyoxovanadate and three acetate ligands. When combined with the photosensitizer [Ru(bpy)₃]²⁺ and the oxidant persulfate, visible‐light‐driven water oxidation with turnover numbers of approximately 1150 and turnover frequencies of about 1.75 s^?1 is observed. Electrochemical, mass‐spectrometric, and spectroscopic studies provide insight into the cluster stability and reactivity. This compound could serve as a model for the molecular structure and reactivity of the OEC and for heterogeneous metal oxide water‐oxidation catalysts.     

Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV₁₄O₄₀]^8? (in short V₁₄) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V₁₄ system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.     

Molecular turnover time of soil organic matter in particle‐size fractions of an arable soil

The composition and molecular residence time of soil organic matter (SOM) in four particle‐size fractions (POM >200 µm, POM 63–200 µm, silt and clay) were determined using Curie‐point pyrolysis/gas chromatography coupled on‐line to mass spectrometry. The fractions were isolated from soils, either continuously with a C₃ wheat (soil ¹³C value = ?26.4‰), or transferred to a C₄ maize (soil ¹³C value = ?20.2‰) cropping system 23 years ago. Pyrograms contained up to 45 different pyrolysis peaks; 37 (ca. 85%) were identifiable compounds. Lignins and carbohydrates dominated the POM fractions, proteins were abundant, but lignin was (nearly) absent in the silt and clay fractions. The mean turnover time (MRT) for the pyrolysis products in particulate organic matter (POM) was generally <15 years (fast C pool) and 20–300 years (medium or slow C pools) in silt and clay fractions. Methylcyclopentenone (carbohydrate) in the clay fraction and benzene (mixed source) in the silt fraction exhibited the longest MRTs, 297 and 159 years, respectively. Plant‐derived organic matter was not stored in soils, but was transformed to microbial remains, mainly in the form of carbohydrates and proteins and held in soil by organo‐mineral interactions. Selective preservation of plant‐derived OM (i.e. lignin) based on chemical recalcitrance was not observed in these arable soils. Association/presence of C with silt or clays in soils clearly increased MRT values, but in an as yet unresolved manner (i.e. ‘truly’ stabilized, or potentially still ‘labile’ but just not accessible C). Copyright © 2009 John Wiley & Sons, Ltd.     

Highly Dispersed Polyoxometalate‐Doped Porous Co3O4 Water Oxidation Photocatalysts Derived from POM@MOF Crystalline Materials

Rational design of earth‐abundant photocatalysts is an important issue for solar energy conversion and storage. Polyoxometalate (POM)@Co₃O₄ composites doped with highly dispersive molecular metal–oxo clusters, synthesized by loading a single Keggin‐type POM cluster into each confined space of a metal–organic framework (MOF), exhibit significantly improved photocatalytic activity in water oxidation compared to the pure MOF‐derived nanostructure. The systematic synthesis of these composite nanocrystals allows the conditions to be tuned, and their respective water oxidation catalytic performance can be efficiently adjusted by varying the thermal treatment temperature and the feeding amount of the POM. This work not only provides a modular and tunable synthetic strategy for preparing molecular cluster@TM oxide (TM=transition metal) nanostructures, but also showcases a universal strategy that is applicable to design and construct multifunctional nanoporous metal oxide composite materials.     

Formation of Thiosemicarbazone‐Functionalized Complexes with (GeS2)2 and (SnS2)2 Units

By reaction of organo‐functionalized germanium or tin sesquisulfides [(R¹T)₄S₆] (T = Ge, Sn; R¹ = CMe₂CH₂COMe) with thiosemicarbazide or its methyl or phenyl derivative, a series of four compounds were obtained and structurally characterized that are based on an inorganic (TS₂)₂ unit with an extended organic chelate ligand CMe₂CH₂CMeNNCSNHR′ (R′ = H, Me, Ph). The products combine a small, reactive metal chalcogenide moiety with a ligand system that allows for a variety of directed extensions at the terminal NHR′ group. Thus, this work represents the starting point to a multifaceted consecutive chemistry involving both the extension of the binary inorganic unit and further derivatization and/or coordination of the organic ligands.     

An Above‐Room‐Temperature Ferroelectric Organo–Metal Halide Perovskite: (3‐Pyrrolinium)(CdCl3)

Hybrid organo–metal halide perovskite materials, such as CH₃NH₃PbI₃, have been shown to be some of the most competitive candidates for absorber materials in photovoltaic (PV) applications. However, their potential has not been completely developed, because a photovoltaic effect with an anomalously large voltage can be achieved only in a ferroelectric phase, while these materials are probably ferroelectric only at temperatures below 180 K. A new hexagonal stacking perovskite‐type complex (3‐pyrrolinium)(CdCl₃) exhibits above‐room‐temperature ferroelectricity with a Curie temperature T_c=316 K and a spontaneous polarization P_s=5.1 μC cm^?2. The material also exhibits antiparallel 180° domains which are related to the anomalous photovoltaic effect. The open‐circuit photovoltage for a 1 mm‐thick bulky crystal reaches 32 V. This finding could provide a new approach to develop solar cells based on organo–metal halide perovskites in photovoltaic research.