Reactivity control of nitrate-incorporating octadecavanadates by changing the oxidation state and metal substitution.

Clarification and control of the active sites at the atomic/molecular level are important to develop nanocatalysts. The catalytic performance of two oxidation states of nitrate-incorporating octadecavanadates, [V18O46(NO3)]5- (V18) and [V18O46(NO3)]4- (V18ox), and a copper-substituted one, [Cu2V16O44(NO3)]5- (Cu2V16), in selective oxidation was investigated. Both V18 and V18ox possessed the same double-helical structures and one of two tetravalent vanadium sites of V18 was oxidized in V18ox. The comparison of the mobility of the incorporated nitrate reveals that tetravalent vanadium centres show stronger interaction with the incorporated anions than pentavalent ones. The oxidation reaction with V18ox proceeded more smoothly with tert-BuOOH as an oxidant than that with V18. The reactivity and selectivity of the oxidation of 2-cyclohexen-1-ol were different among the derivatives. V18ox showed the higher reactivity with 72% selectivity to epoxide. With V18, reactivity was lower but higher selectivity to epoxide was achieved. In the presence of Cu2V16, 2-cyclohexen-1-one was selectively obtained with 81% selectivity. The order of the reactivity for cyclooctene was V18ox, V18 and Cu2V16. These results shows that the cap part of the double-helix acts as the active site. Even though the vanadium-oxygen species exhibit the same structures, the catalytic properties can be controlled by changing the valence of vanadium and metal substitution.

Mechanistic insights into template-driven polyoxovanadate self-assembly: the role of internal and external templates.

The self-assembly of molecular metal oxides, polyoxometalates (POMs), can be controlled using internal or, more rarely, external templates. Here, we explore how the interplay between internal templates (halides, oxoanions) and organic external templates (protonated cyclene species) affect the self-assembly of a model polyoxovanadate cluster, [V12O32X]n- (X = Cl-, Br-, NO3-). A combination of crystallographic analyses, spectroscopic studies and in situ as well as solid-state 51V NMR spectroscopy provide critical insights into the initial formation of an intermediate vanadate species formed during the process. Structural and spectroscopic studies suggest that a direct interaction between internal and external templates allows tuning of the internal template position within the cluster cavity. These insights form the basis for further developing the template-driven synthetic chemistry of polyoxovanadates.

Vanadium-substituted polycationic Al-oxo cluster in a porous ionic crystal exhibiting Lewis acidity.

Herein we present the first example of a vanadium-substituted δ-Keggin Al13-based (Al28V4) porous Ionic crystal (PIC) (Al28V4-PW9V3). Structural and theoretical studies suggested that Al28V4 may exhibit Lewis acidity, which was confirmed by acetalization reaction with Al28V4-PW9V3 as a solid catalyst and investigations with pyridine or 2,6-lutidine as basic probe molecules. A comparative study with the δ-Keggin Al13 monomer based PIC indicated that the vanadium-substitution gave rise to the Lewis acidity.

Basicity of isostructural porous ionic crystals composed of Nb/Ta-substituted Keggin-type polyoxotungstates.

Three isostructural porous ionic crystals (PICs) based on Keggin-type POMs with different compositions but equal negative charge ([BW12O40]5- (BW12), [SiW11NbO40]5- (SiW11Nb), and [SiW11TaO40]5- (SiW11Ta)) are synthesized. Experimental and theoretical characterizations of the three PICs (1_BW12, 1_SiW11Nb, and 1_SiW11Ta) show that the substitution of Nb/Ta for W in the POMs enhances the basicity of PICs, which increases in the order of 1_BW12 < 1_SiW11Nb < 1_SiW11Ta. These findings clearly show that the increase in basicity is due not only to the increase in negative charge of the POM molecule as is often explained, but also to the character of the substituted element itself.

Incorporating highly basic polyoxometalate anions comprising Nb or Ta into nanoscale reaction fields of porous ionic crystals.

Polyoxometalates (POMs) are oxide cluster anions composed of high-valence early transition metals and are widely used as catalysts. Yet base catalysis of POMs remains an ongoing challenge; group V (V, Nb, and Ta) elements form more negatively charged POMs than group VI (Mo and W) elements, and in particular, polyoxoniobates and polyoxotantalates are known to show strong basicity in solution due to the highly negative surface oxygen atoms. Herein, we report for the first time porous ionic crystals (PICs) comprising Nb or Ta. The PICs are composed of Dawson-type Nb/W or Ta/W mixed-addenda POMs with oxo-centered trinuclear CrIII carboxylates and potassium ions as counter cations to control the crystal structure. Among the PICs, those with Nb or Ta tri-substituted POMs exhibit the highest yield (78-82%) and selectivity (99%) towards the Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate (353 K, 6 h), which is a typical base-catalyzed reaction, as reusable solid catalysts, and they can also catalyze the reaction of other active methylene compounds. A detailed investigation into the crystal structures together with DFT calculations and in situ IR spectroscopy with methanol as a basic probe molecule shows that the exposure of [Nb3O13] or [Ta3O13] units with highly negative surface oxygen atoms to the pore surface of PICs is crucial to the catalytic performance. These findings based on the composition-structure-function relationships show that Nb- and Ta-containing PICs can serve as platforms for rational designing of heterogeneous base catalysts.

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.

Synthesis of cyanooxovanadate and cyanosilylation of ketones.

The cyanosilylation was performed by using metavanadate catalysts, and in situ measurements revealed the formation of [VO2(CN)3]2- and [VO4TMS2]- under reaction conditions. The reaction of [VO2(CN)3]2-, trimethylsilyl cyanide (TMSCN), and water afforded [VO4TMS2]- and CN-, which reacted with ketones to yield the corresponding cyanohydrin trimethylsilyl ethers over [VO2(CN)3]2-. Compound [VO2(CN)3]2- showed high catalytic performance for cyanosilylation of various carbonyl compounds. In the case of n-hexanal, turnover frequency reached up to 250 s-1.

Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage.

A calix-shaped polyoxometalate, [V12O32]4- (V12), stabilizes an anion moiety in its central cavity. This molecule-sized container has the potential to control the reactivity of an anion. The highly-reactive cyanate is smoothly trapped by V12 to form [V12O32(CN)]5-. In the CH3NO2 solution, cyanate abstracts protons from CH3NO2, and the resultant CH2NO2- is stabilized in V12 to form [V12O32(CH2NO2)]5- (V12(CH2NO2)). A crystallographic analysis revealed the double-bond characteristic short bond distance of 1.248 Å between the carbon and nitrogen atoms in the nitromethane anion in V12. 1H and 13C NMR studies showed that the nitromethane anion in V12 must not be exchanged with the nitromethane solvent. Thus, the V12 container restrains the reactivity of anionic species.

Induced Fitting and Polarization of a Bromine Molecule in an Electrophilic Inorganic Molecular Cavity and Its Bromination Reactivity.

Dodecavanadate, [V12 O32 ]4- (V12), possesses a 4.4 Šcavity entrance, and the cavity shows unique electrophilicity. Owing to the high polarizability, Br2 was inserted into V12, inducing the inversion of one of the VO5 square pyramids to form [V12 O32 (Br2 )]4- (V12(Br2)). The inserted Br2 molecule was polarized and showed a peak at 185 cm-1 in the IR spectrum. The reaction of V12(Br2) and toluene yielded bromination of toluene at the ring, showing the electrophilicity of the inserted Br2 molecule. Compound V12(Br2) also reacted with propane, n-butane, and n-pentane to give brominated alkanes. Bromination with V12(Br2) showed high selectivity for 3-bromopentane (64 %) among the monobromopentane products and preferred threo isomer among 2-,3-dibromobutane and 2,3-dibromopenane. The unique inorganic cavity traps Br2 leading the polarization of the diatomic molecule. Owing to its new reaction field, the trapped Br2 shows selective functionalization of alkanes.

Isostructural mesoporous ionic crystals as a tunable platform for acid catalysis.

Eleven isostructural mesoporous ionic crystals (meso-PICs) are synthesized. The initial activities of the Barbier-Grignard reaction, which is a typical C-C bond formation reaction, catalyzed by the meso-PICs are dependent on the acid dissociation constant of the aqua ions of Mn+ and the types of polyoxometalates, which construct the meso-PICs.

Evaluation of the chemo- and shape-selective association of a bowl-type dodecavanadate cage with an electron-rich group.

The host-guest interaction between a half spherical-type dodecavanadate (V12) and a neutral molecule guest was evaluated by monitoring the flip of a VO5 unit caused by the presence or absence of a guest in the cavity of V12. In N,N-dimethylformamide (DMF), V12 adopted the guest-free form (V12-free). By the addition of several guest molecules, such as acetonitrile, nitromethane, and dichloromethane, the structural conversion to the guest-inserted form (V12(guest)) was observed with the affinity constants of 137 ± 10 M-1, 0.14 ± 0.1 M-1, and 0.15 ± 0.1 M-1, respectively. In the case of 1,2-dichloroethane, 1,2-dibromoethane, and 1,2-diiodoethane, the constants were 35 ± 5 M-1, 114 ± 5 M-1, and 2.1 ± 0.5 M-1, respectively, suggesting that the bromo group is the best fit to the cavity of the bowl. A cyclic carbonate, 5- and 6-membered lactones, cyclobutanone, and hexanal were inserted into the V12 host, while a non-cyclic carbonate, non-cyclic and 7-membered cyclic ester, a ketone with a 5-membered ring, and benzaldehyde showed no effect on the guest insertion. The V12 host preferred to hold a guest with an electron-rich group, and the bowl-type structure showed the unique shape-selective interaction with the guest.

Synthesis and structural characterization of tube-type tetradecavanadates.

By the reaction of ammonium perchlorate with anion-incorporated bowl-type dodecavanadates, viz. [V12O32(X)]5- [X = N3- (1), OCN- and NO3-], tube-type tetradecavanadates, viz. (NH4)7[V14O38(X)] [X = N3- (2), OCN- (3) and NO3- (4)] were synthesized. The crystal structures of penta(tetraethylammonium) azidododecavanadate nitromethane monosolvate, (C8H20N)5[V12O32(N3)]·CH3NO2, 1, heptaammonium azidotetradecavanadate dimethyl sulfoxide hexasolvate, (NH4)7[V14O38(N3)]·6C2H6OS, 2, heptaammonium cyanatotetradecavanadate dimethyl sulfoxide hexasolvate, (NH4)7[V14O38(OCN)]·6C2H6OS, 3, and heptaammonium nitratotetradecavanadate dimethyl sulfoxide hexasolvate, (NH4)7[V14O38(NO3)]·6C2H6OS, 4, were determined. The tube consists of two layers of V7 rings with a guest anion at the centre. The distances between the incorporated anions and the nearest V atoms are 3.058 (3), 3.039 (6) and 2.811 (9) Šfor 2, 3 and 4, respectively, showing that the incorporated anions are stabilized via noncovalent interactions. Two ammonium cations cap both ends of the tube to stabilize the structures via hydrogen-bonding interactions. Linear OCN- and N3- anions sit on the twofold rotation axes of the tube frameworks and the triangular plane of the NO3- anion deviates from the equatorial plane of the tube by ca 30°.

Solid-State Umbrella-type Inversion of a VO5 Square-Pyramidal Unit in a Bowl-type Dodecavanadate Induced by Insertion and Elimination of a Guest Molecule.

Design of cavities for a target molecule and the elucidation of the corresponding host-guest interactions are important for molecular manipulation. A discrete dodecavanadate bowl, [V12 O32 ]4- (V12), with an entrance diameter of 4.4 Šand an electron-rich guest at the center of the bowl, was stabilized by electrostatic interactions. A characteristic of V12 is a solid-state polytopal rearrangement during guest elimination and recapture. A guest-free dodecavanadate, [V12 O32 ]4- (V12-free), was prepared by removal of the guest from CH2 Cl2 -inserted V12 under vacuum at 50 °C. Single-crystal X-ray analysis revealed that one of the VO5 square pyramids at the bottom of V12-free was inverted to fill the void of the bowl cavity. The exposure of V12-free to the guest molecule vapors of CH2 Cl2 , 1,2-dichloroethane, MeNO2 , MeCN, and MeBr resulted in the selective insertion of the guest to reform the guest-inserted V12 structure. Whereas CO2 could be inserted in the V12 bowl, CH4 and CO could not.

Small-Molecule Anion Recognition by a Shape-Responsive Bowl-Type Dodecavanadate.

A dodecavanadate, [V12 O32 ]4- , is an inorganic bowl-type host with a cavity entrance with a diameter of 4.4 Šin the optimized structure. Linear, bent, and trigonal planar anions are tested as guest anions and the formation of host-guest complexes, [V12 O32 (X)]5- (X=CN- , OCN- , NO2- , NO3- , HCO2- , and CH3 CO2- ), were confirmed by X-ray crystallographic analyses and a 51 V NMR spectroscopy study. The degree of distortion of the bowl from a regular to an oval shape depends on the type of guest anion. In 51 V NMR spectroscopy, all chemical shifts of the host-guest complexes are clearly shifted after guest incorporation. The incorporation reaction rates for OCN- , NO2- , HCO2- , and CH3 CO2- are much larger than those of NO3- and halides. The incorporated nonspherical molecular anions in the dodecavanadate host are easily dissociated or exchanged for other anions, whereas spherical halides in the host are preserved without dissociation, even in the presence of the tested anions.

A Bowl-Type Dodecavanadate as a Halide Receptor.

The dodecavanadate framework, [V12O32]4-, exhibits a unique bowl-type structure with an open molecular oxide cage having a cavity diameter of 4.4 Å, and different synthetic paths were required to construct the bowl-type structure with a different guest. A new dodecavanadate, {(n-C4H9)4N}4[V12O32(CH3NO2)] (1), is synthesized with a nitromethane guest, which is stacked above the entrance of the hemisphere rather than fully occupying the cavity, and it enables a guest-capturing reaction, while retaining the anionic cage structure. Compound 1 is a good precursor for halide-centered dodecavanadates, {(C2H5)4N}5[V12O32(X)] (X = Cl- (2), Br- (3), and I- (4)). The position of the halide inside the cavity correlates with the ionic radius of the guest; the small chloride ion sat at the far bottom, and the large iodide floated at the entrance. The inclusion reaction rates were estimated through 51V NMR time-course measurements in nitromethane. The reaction rates increase in the order I- < Br- < Cl-.

A chloride capturing system via proton-induced structure transformation between opened- and closed-forms of dodecavanadates.

Chloride-incorporated dodecavanadates show two distinct structures of the monoprotonated-form [HV12O32(Cl)](4-) (closed-V12) with a spherical closed-structure and the opened-form [V12O32(Cl)](5-) (opened-V12). The reaction of closed-V12 with a stoichiometric amount of ethylenediamine drives the structure transformation reaction to opened-V12, quantitatively. From time dependent observations of (51)V NMR, a tube-type intermediate [V12O32(Cl)](5-) (tube-V12) was observed in the transformation process. Isolation of the intermediate was achieved by the deprotonation reaction of closed-V12 with diethylamine, and the structure transformation was confirmed by using the isolated intermediate. The reverse transformation from opened-V12 to closed-V12 was also achieved by addition of trifluoroacetic acid. The geometrical difference between closed-V12 and opened-V12 is reflected in the reactivity difference to the external reagents, and this was demonstrated by examining the chloride removal reaction by using a silver cation. The incorporated chloride was preserved in the closed-V12 cage even in the presence of a silver cation. In contrast, the chloride in opened-V12 was removed as AgCl by the silver cation. In addition, by the reaction of chloride-free opened-V12 with a quantitative amount of {Et4N}Cl retrieved opened-V12, showing the capability of opened-V12 to recapture a guest chloride in the cavity. This transformation between two isomeric dodecavanadate structures is regarded as the movement of a molecular mitt to catch a ball and secure it.

Water- and Temperature-Triggered Reversible Structural Transformation of Tetranuclear Cobalt(II) Cores Sandwiched by Polyoxometalates.

Although stimuli-responsive structural transformations of inorganic materials have attracted considerable attention because of their potential use as functional switchable materials, multinuclear metal cores frequently suffer from unexpected dissociation of metal cations and/or irreversible transformations into infinite structures. In this study, we describe the successful demonstration of the water- and temperature-triggered reversible structural transformation between cubane- and planar-type tetranuclear Co(II) cores sandwiched by polyoxometalates. The arrangements and coordination geometries of the Co(II) cations were interconverted by simple hydration and dehydration, resulting in the manipulation of the magnetic and optical properties of these compounds. Moreover, this system showed unique thermochromism through temperature-dependent reversible structural interconversion.

Synthesis and characterization of fluoride-incorporated polyoxovanadates.

The speciation studies of oxovanadates are essential to clarify their biological activities. We surveyed the distribution of oxovanadate species in the presence of halide anions with various acid concentrations in an aqueous mixed-solvent system. The presence of chloride, bromide, and iodide anions has no effects on the appearance of polyoxovanadate species observed in (51)V NMR. Those are the precedent formation of metavanadate species and decavanadates. The presence of fluoride anion during the addition of acids exhibits strong intervention in the polyoxovanadate equilibria and we found the subsequent formation of two polyoxovanadate species by (51)V NMR observation. From the estimated experimental condition, we isolated fluoride-incorporated polyoxovanadates {Et4N}4[V7O19F] and {Et4N}4[HV11O29F2], successfully. Polyanion [V7O19F](4-) is the fluoride-incorporated all V(V) state polyoxovanadate which has two different coordination environments of tetrahedral and square pyramidal vanadium units within the one anionic structural integrity. The structural gap between tetrahedral-unit-based metavanadate and octahedral-unit-based decavanadate structures may be linked by this hybrid complex.

Visible-light-induced photoredox catalysis with a tetracerium-containing silicotungstate.

The development of visible-light-induced photocatalysts for chemoselective functional group transformations has received considerable attention. Polyoxometalates (POMs) are potential materials for efficient photocatalysts because their properties can be precisely tuned by changing their constituent elements and structures and by the introduction of additional metal cations. Furthermore, they are thermally and oxidatively more stable than the frequently utilized organometallic complexes. The visible-light-responsive tetranuclear cerium(III)-containing silicotungstate TBA6[{Ce(H2O)}2{Ce(CH3CN)}2(µ4-O)(γ-SiW10O36)2] (CePOM; TBA=tetra-n-butylammonium) has now been synthesized; when CePOM was irradiated with visible light (λ>400 nm), a unique intramolecular Ce(III)-to-POM(W(VI)) charge transfer was observed. With CePOM, the photocatalytic oxidative dehydrogenation of primary and secondary amines as well as the α-cyanation of tertiary amines smoothly proceeded in the presence of O2 (1 atm) as the sole oxidant.

Synthesis, structure characterization, and reversible transformation of a cobalt salt of a dilacunary γ-Keggin silicotungstate and sandwich-type di- and tetracobalt-containing silicotungstate dimers.

A cobalt salt of a γ-Keggin dilacunary silicotungstate, {CoL5}2[γ-SiW10O34L2] [Co-SiW10; L = N,N-dimethylformamide (DMF) or H2O], could be synthesized by the cation-exchange reaction of TBA4[γ-H4SiW10O36] (TBA = tetra-n-butylammonium) with 2 equiv of Co(NO3)2 with respect to TBA4[γ-H4SiW10O36] in a mixed solvent of DMF and acetone (97% yield). Each Co-SiW10 was linked by water molecules via a hydrogen-bonding network. Besides Co-SiW10, various kinds of isostructural M-SiW10 could be synthesized via the same procedure as that for Co-SiW10 (M = Mn(2+), Fe(2+), Ni(2+), Cu(2+), Zn(2+), and Cd(2+)). By the reaction of Co-SiW10 with 1 equiv of TBA6[γ-H2SiW10O36] in acetone, a silicotungstate dimer pillared by two cobalt cations with a significantly slipped dimer configuration, TBA6[Co2(γ-H3SiW10O36)2]·3H2O (Co2), could be synthesized. By the reaction of Co-SiW10 with 3 equiv of TBAOH in acetone, a tetracobalt-containing sandwich-type silicotungstate, TBA6[{Co(H2O)}2(µ3-OH)2{Co(H2O)2}2(γ-H2SiW10O36)2]·5H2O (Co4), could be synthesized. Compound Co4 possessed the tetracobalt-oxygen core, [{Co(H2O)}2(µ3-OH)2{Co(H2O)2}2](6+), identical with those of previously reported Weakley-type sandwich polyoxometalates, [Co4(H2O)2(XM9O34)2](n-) (X = P(5+), Si(4+), Ge(4+), As(5+) or V(5+); M = Mo(6+) or W(6+)). The reversible transformation between these three compounds (Co-SiW10 ⇆ Co2, Co-SiW10 ⇆ Co4, and Co2 ⇆ Co4) took place by the addition and/or subtraction of required components in appropriate solvents, affording the desired products in high yields (71-93% yields).