Acid–base catalyses by dimeric disilicoicosatungstates and divacant γ-Keggin-type silicodecatungstate parent: Reactivity of the polyoxometalate compounds controlled by step-by-step protonation of lacunary WO sites

The catalytic properties of disilicoicosatungstates, [{γ-SiW₁₀O₃₂(H₂O)₂}₂(μ-O)₂]⁴⁻ (2) and [H(γ-SiW₁₀O₃₂)₂(μ-O)₄]⁷⁻ (3), and their parent divacant γ-Keggin type silicodecatungstate, [γ-SiW₁₀O₃₄(H₂O)₂]⁴⁻ (1), toward C–C bond formation reactions have been investigated. The disilicoicosatungstate 2 with aquo ligands exhibits the acidic nature and catalyzes the Mukaiyama-aldol condensation and carbonyl-ene reaction, while 1 and 3 are rather basic and catalyze the Knoevenagel condensation. Therefore, the acid–base properties of a series of lacunary γ-Keggin silicotungstate derivatives 1–3 are clearly different, and the catalyses of 1–3 depend on the molecular structures while 1–3 are composed of a common [SiW₁₀O₃₂] fragment.     

Density functional study of the roles of chemical composition of di-transition-metal-substituted gamma-Keggin polyoxometalate anions

The roles of chemical composition (X, M and M(FW)) of di-transition-metal-substituted gamma-Keggin polytungstates and polymolybdates, [(X(n)(+)O(4))M(2)(OH)(2)(M(FW))(10)O(32)]((8-n)-), on the geometry, electronic structure, and magnetic properties of these species have been investigated at the density functional level. It was shown that the change of the heteroatom X via Al(III)-Si(IV)-P(V)-S(VI) slightly stabilizes the broken-symmetry (BS) state over the high-spin (HS) state, increases the antiferromagnetic coupling constant, J, of these species, and lowers the energies of their highest-occupied molecular orbitals (HOMOs) and lowest-unoccupied molecular orbitals (LUMOs). The change of the redox-active center M from Mn to Fe slightly increases the M-(XO(4)) interaction, J-coupling constant, and energy gap between the HS and BS states. Meanwhile, the LUMOs are stabilized, indicating the stronger oxidant character of [(X(n)(+)O(4))M(2)(OH)(2)W(10)O(32)]((8-n)-) for M = Fe than Mn. It was shown that the change of addenda atom M(FW) from W to Mo makes (a) the geometry of Keggin "cage" slightly smaller, (b) the interaction of redox-active centers (Fe) with the central XO(4)-unit slightly stronger, and (c) the J-coupling constant, as well as the energy gap DeltaE(BS-HS), slightly larger.     

New polyoxometalate compounds built up of lacunary Wells-Dawson anions and trivalent lanthanide cations

Five new polyoxometalate compounds built on lacunary Wells-Dawson anions and trivalent lanthanide cations, KNa3[Nd2(H2O)10(alpha2-P2W17O61)].11H2O (1), (H3O)[Nd3(H2O)17(alpha2-P2W17O61)].6.75H2O (2), (H2bpy)2[Nd2(H2O)9 (alpha2-P2W17O61)].4.5H2O (3), (H2bpy)2[La2(H2O)9(alpha2-P2W17O61)].4.5H2O (4), and (H2bpy)2[Eu2(H2O)9(alpha2-P2W17O61)].5H2O (5), have been synthesized and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. Compound 1 shows a bisupporting polyoxometalate cluster structure where two {Nd(H2O)7}3+ fragments are supported on the polyoxometalate dimer [{Nd(H2O)3(alpha2-P2W17O61)}2]14-; this represents the first bisupporting polyoxometalate compound based on a polyoxometalate dimer. Compound 2 displays a 1D chain structure built up of bisupporting polyoxoanions [{Nd(H2O)7}2{Nd(H2O)3(alpha2-P2W17O61)}2]8- and Nd3+ ions. Compounds 3-5 are isostructural and show a 2D structure constructed of 1D polyoxometalate chains of [Ln(H2O)2(alpha2-P2W17O61)]n(7n-) linked by Ln3+ ions. Compounds 2-5 represent the first extended structures formed by lacunary Wells-Dawson anions and trivalent lanthanide ions. The influence of the Ln3+/[alpha2-P2W17O61]10- ratio on the syntheses of these five compounds has been studied. Furthermore, the fluorescent activity of compound 5 is reported.     

Mesomorphic structures of protonated surfactant-encapsulated polyoxometalate complexes

Keggin-type heteropolyanions, H(3)PW(12)O(40) (HPW), Na(3)PW(12)O(40) (NaPW), H(4)SiW(12)O(40) (HSiW) and K(4)SiW(12)O(40) (KSiW), were encapsulated by a cationic surfactant, di[12-(4'-octyloxy-4-azophenyl)dodecyloxy]dimethylam monium bromide (L), through the replacement of counterions. The resulting surfactant-encapsulated polyoxometalate complexes were characterized by UV-vis, Raman, and NMR spectra in detail. The measurement results indicated that some azobenzene groups of the surfactant were protonated in the complexes HL/HPW (HL is the abbreviation of the protonated surfactant), HL/NaPW, and HL/HSiW during the process of encapsulation, whereas the protonation was not observed in L/KSiW. The thermotropic liquid crystal properties of these complexes were investigated by differential scanning calorimetry, polarized optical microscopy and variable-temperature X-ray diffraction. Interestingly, different smectic mesophases were observed between the protonated HL/HSiW and the non-protonated L/KSiW, which suggests that the protonation of azobenzene groups in HL/HSiW plays a key role in the liquid crystalline organization. However, protonated HL/HPW and HL/NaPW exhibit a similar smectic B phase to that of the de-protonated one, L/HPW. A competitive balance between the phase separation and the volume minimization of surfactants was proposed to explain the self-organized liquid crystal structures of these protonated and non-protonated complexes. To the best of our knowledge, the present investigation provides a specific example for protonated hybrid materials with stable liquid crystal properties.     

Recognition of anions by protonated methylazacalixpyridines

Methylazacalixpyridines are a unique kind of macrocyclic molecules that are able to self-regulate their conformations to best fit the guests. They had shown good recognition to both neutral molecules such as diols and fullerenes and cations. After protonation, the conformation of methylazacalixpyridines became more flexible and could serve as receptors for anions. In the solution, the protonated methylazacalix[2]pyridine[2]arene formed complexes with halides yielding biding constants of 79 (mol/L)⁻¹ for chloride, 10 (mol/L)⁻¹ for bromide, and 79 (mol/L)⁻¹ for iodide, respectively. The crystal structures of the complexes between protonated methylazacalix[4]pyridine (MACP-4), methylazacalix[2]pyridine[2]arene (MACP-2-A-2), and iodide anion showed a multiple interaction mode including electrostatic attraction, hydrogen bonding, and anion-π interaction     

Voltammetric studies on the reduction of polyoxometalate anions in ionic liquids

The electrochemical reduction of tetrabutylammonium salts of isostructural pairs of polyoxometalates [Bu4N]2[M6O19], [Bu4N]4[alpha-SiM12O40], and [Bu4N]4[alpha-S2M18O62] (M = Mo or W) has been investigated at glassy carbon electrodes in dissolved and surface-confined states in ionic liquids and other media. In the ionic liquid 1-n-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF(6)], between two and six reversible one-electron-transfer processes were detected. Detailed studies on the process [alpha-S2W18O62](4-/5-) in a range of ionic liquids, water, and conventional organic solvents (containing 0.1 M electrolyte) suggest that the polarity of the medium plays a key role in the determination of the reversible potential. Reduction processes involving very highly charged [alpha-S2W18O62](8-/9-/10-) species are strongly influenced by the purity of the medium.     

Preparation of MCM-41 incorporated with lacunary Keggin polyoxometalate and its catalytic performance in esterification

The ordered mesoporous MCM-41 materials incorporated with lacunary polyoxometalate were prepared via an original direct synthesis method. As the control, the samples with similar lacunary polyoxometalate loadings were also prepared by impregnation of MCM-41. The prepared samples were characterized by XRF, XRD, FT-IR, Raman spectra, HRTEM, SEM, N(2) adsorption isotherm, TG-DTA, and NH(3)-TPD technology. The results show that the lacunary polyoxometalate is better dispersed in the direct synthesized samples than in the impregnated samples, and its structure remains intact after formation of the materials. The catalytic performance of the materials was tested using the esterification of n-butanol with acetic acid. The direct synthesized samples display excellent catalytic performance and reusability, which is superior to the impregnated samples. Under the optimized conditions, the conversion of n-butanol is 89.7%, and the selectivity of butyl acetate is nearly 100%.     

Novel cerium(IV) heteropolyoxotungstate containing two types of lacunary Keggin anions

A novel V-shaped polyoxotungstate is formed when Ce(IV) metal centres bridge monolacunary [PW(11)O(39)](7-) anions to an unusual 1,4-bilacunary [PW(10)O(38)](11-) anion which appears with an unprecedented bridging structural motif.     

Computational study on the ring-opening reaction of protonated oxirane and methylpropene

A computational study on the intermolecular reaction of protonated oxirane with methylpropene, as a model for initiation of oxidosqualene cyclisation, shows that the S_N2-like ring opening is strongly exothermic with a low barrier to reaction and establishes the geometry of the intermolecular reaction.     

On the origin of alternating bond distortions and the emergence of chirality in polyoxometalate anions

Alternating short and long bond length (ABL) distortions observed within the ring structures of molecular metal oxide anions or polyoxometalates (POMs) are reminiscent of the cooperative linear ABL distortions in perovskite d(0) metal oxides. We show herein that these distortions have a common origin: a pseudo Jahn-Teller (PJT) vibronic instability. Four POM structural types with different M(n)O(n) ring sizes are investigated herein using density functional theoretical methods: Lindqvist [M6O19](q-) (n = 4), Keggin alpha-[XM12O40](q-) (n = 6), Wells-Dawson alpha-[X2M18O62](q-) (n = 8), and Preyssler [(Na)P5W30O110](14-) (n = 10), where M = Mo(VI) and W(VI) and X = Si(IV), Ge(IV), P(V), As(V), S(VI), and Se(VI). Chirality is induced within the latter three structural types by the ABL ring distortions. The calculations confirm the PJT vibronic origin of the ABL distortions with good agreement between calculated geometries and published single-crystal X-ray diffraction data. Both theory and experiment show that the vibronic interaction and distortion magnitude increase for (1) molybdates relative to that of tungstates, (2) larger M(n)O(n) ring sizes, (3) increases in negative charge of the internalized fragments (O(2-) or XO4(q-)), and (4) d(0) versus d(n) metal oxidation states. The PJT vibronic coupling model explains these observations in terms of the energy gap between Kohn-Sham frontier molecular orbitals (MOs) concomitant with the propensity for metal-oxygen pi-bonding within the M(n)O(n) rings. The frontier MOs for the undistorted nuclear configurations are largely nonbonding pi-O(p) (occupied) and pi-M(d) (unoccupied) in character, where smaller HOMO-LUMO (H-L) gap energies lead to greater metal-oxygen pi-orbital mixing under the influence of the nuclear distortion. A reduction in pi-bond order decreases the distortion in mixed-valence POMs. Of the tungstates examined, only the Preyssler anion shows pronounced ABL ring distortions, which derive from its large ring size and concomitant small H-L gap.     

Structural and dynamical aspects of alkylammonium salts of a silicodecatungstate as heterogeneous epoxidation catalysts

The structural and dynamical aspects of alkylammonium salts of a silicodecatungstate [(CH(3))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C1], [(n-C(3)H(7))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C3], [(n-C(4)H(9))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C4], and [(n-C(5)H(11))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C5] were investigated. The results of sorption isotherms, XRD analyses, and solid-state NMR spectroscopy show that facile sorption of solvent molecules, flexibility of structures, and high mobility of alkylammonium cations are crucial to the uniform distribution of reactant and oxidant molecules throughout the bulk solid, which are related to the high catalytic activities for epoxidation of alkenes.     

A comparative catalytic study using different metal ions by incorporating functionalized metallosalen into the lacunary position of Keggin polyoxometalate

A series of new hybrids, POM (M-Salen@POM) were synthesized by successfully inserting metallosalen compounds (where M ​= ​Co, Cu, Fe and Ru) into the lacunary position of Keggin type polyoxometalate, K₈SiW₁₁O₃₉ (POM). The hybrids were characterized by FT-IR, powder XRD, diffuse reflectance UV–Vis, energy dispersive X-Ray and inductively coupled plasma atomic emission spectroscopy (ICP) techniques. The hybrids with different metal centers were comparatively studied for their catalytic activity in the oxidation of cycloalkanes, cycloalcohols and alkyl aromatic using a green oxidant, hydrogen peroxide. The products obtained during catalysis were estimated by gas chromatography(GC) and mass spectroscopy(MS). Catalytically synthesized products are of high industrial importance.     

Construction of one Ru2W12-cluster and six lacunary Keggin tungstoarsenate leading to the larger Ru-containing polyoxometalate photocatalyst

Construction of two Ru^Ⅲ cations and six lacunary Keggin fragments resulted in a novel Ru₂W₁₂-cluster {(RuO₆)₂(WO₃)₁₂(H₂O)₁₂} bridged polyoxometalate, NaH₁₁[(RuO₆)(AsW₉O₃₃)₃{(W₆O₃)(H₂O)₆}]₂ 53H₂O (NaH₁₁·1·53H₂O), which represent the largest cluster in all the Ru-containing polyoxometalates. The most interesting characteristic is that the symmetry-related Ru₂W₁₂-cluster-based hexamers contain two windmill-shaped [(RuO₆)(AsW₉O₃₃)₃{(W₆O₃)(H₂O)₆}] trimers or the Ru₂W₁₂ cluster was tightly wrapped by six segments of B-β-AsW₉O₃₃. The other remarkable feature is that there have one intriguing cubane structure: which is composed of the Ru(1, 2) and W(1, 28, 50, 51, 52, 53) atoms. The oxygenation reactions of anilines to azoxybenzenes was evaluated when NaH₁₁·1·53H₂O served as effective catalyst by probing various reaction. The inherent redox property of oxygen-rich polyoxometalate surfaces and high photocatalytic activity of the Ru-containing metal cluster imbedded in NaH₁₁·1·53H₂O provide sufficient driving force for the photocatalytic transformation from anilines to azoxybenzenes. The oxidation of anilines can be realized with higher selectivity to afford various azoxybenzene compounds. The durability test shows that Ru-doping catalyst displays excellent chemical stability during the photocatalytic process.     

Gas-phase ion/ion reactions of multiply protonated polypeptides with metal containing anions

Gas-phase reactions of multiply protonated polypeptides and metal containing anions represent a new methodology for manipulating the cationizing agent composition of polypeptides. This approach affords greater flexibility in forming metal containing ions than commonly used methods, such as electrospray ionization of a metal salt/peptide mixture and matrix-assisted laser desorption. Here, the effects of properties of the polypeptide and anionic reactant on the nature of the reaction products are investigated. For a given metal, the identity of the ligand in the metal containing anion is the dominant factor in determining product distributions. For a given polypeptide ion, the difference between the metal ion affinity and the proton affinity of the negatively charged ligand in the anionic reactant is of predictive value in anticipating the relative contributions of proton transfer and metal ion transfer. Furthermore, the binding strength of the ligand anion to charge sites in the polypeptide correlates with the extent of observed cluster ion formation. Polypeptide composition, sequence, and charge state can also play a notable role in determining the distribution of products. In addition to their usefulness in gas-phase ion synthesis strategies, the reactions of protonated polypeptides and metal containing anions represent an example of a gas-phase ion/ion reaction that is sensitive to polypeptide structure. These observations are noteworthy in that they allude to the possibility of obtaining information, without requiring fragmentation of the peptide backbone, about ion structure as well as the relative ion affinities associated with the reactants.     

Computational modeling of nanorod growth

In this computational study, we used molecular dynamics and the embedded atom method to successfully reproduce the growth of gold nanorod morphologies from starting spherical seeds in the presence of model surfactants. The surfactant model was developed through extensive systematic attempts aimed at inducing nonisotropic nanoparticle growth in strictly isotropic computational growth environments. The aim of this study was to identify key properties of the surfactants which were most important for the successful anisotropic growth of nanorods. The observed surface and collective dynamics of surfactants shed light on the likely growth phenomena of real nanoprods. These phenomena include the initial thermodynamically driven selective adsorption, segregation, and orientation of the surfactant groups on specific crystallographic surfaces of spherical nanoparticle seeds and the kinetic elongation of unstable surfaces due to growth inhibiting surfactants on those surfaces. Interestingly, the model not only reproduced the growth of nearly all known nanorod morphologies when starting from an initial fcc or fivefold seed but also reproduced the experimentally observed failure of nanorod growth when starting from spherical nanoparticles such as the I(h) morphology or morphologies containing a single twinning plane. Nanorod morphologies observed in this work included fivefold nanorods, fcc crystalline nanorods in the [100] direction and [112] directions and the more exotic "dumbell-like" nanorods. Non-nanorod morphologies observed included the I(h) and the nanoprism morphology. Some of the key properties of the most successful surfactants seemed to be suggestive of the important but little understood role played by silver ions in the growth process of real nanorods.     

Computational modeling of extended systems

Advancements in computing architecture and in theoretical techniques allow for the modeling of complex, extended systems. This section of the 50th anniversary issue of Theoretical Chemistry Accounts highlights modeling work performed on nanostructured systems and underscores the enormous potential for synergy between theory and experiment in modern nanoscience.     

Computational modeling of amorphous silica. 2. Modeling the initial structures. Aerosil

A qualitative algorithm for constructing large clusters of aerosil model structures is used. According to this algorithm and the classification of amorphous silicas, aerosil is classified with tectosilicas, which are characterized by close packing of silicon-oxygen tetrahedra. Two quantitative algorithms for constructing large close-packed clusters are proposed. The structures of the clusters having from 10 to 24 silicon atoms, completely optimized by quantum chemical methods, were obtained. Small, medium, and large clusters for modeling the local and collective properties of atomic and functional group packing in the aerosil structure are distinguished. Institute of Surface Chemistry, Ukrainian Academy of Sciences. Russian University of Peoples' Friendship. Translated fromZhurnal Struktumoi Khimii, Vol. 35, No. 3, pp. 16–26, May–June, 1994. Translated by O. Kharlamova     

Computational modeling of amorphous silica. 4. Modeling the initial structures. Aerogel

A qualitative classification algorithm for constructing large clusters of aerogel model structures is used. According to this algorithm, aerogel is classified with polysilicas characterized by a packing of long chains of silicon-oxygen tetrahedra. A model of the aerogel structure is suggested, according to which aerogel is described as a set of cross-linked chains forming double or more complex ribbons. This model is in agreement with the conclusions drawn from analysis of the vibration spectra of its components. Institute of Surface Chemistry, Ukrainian Academy of Sciences. Russian University of Peoples' Friendship. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 3, pp. 35–38, May–June, 1994. Translated by O. Kharlamova     

Computational prediction of trends in the selectivity of macrocyclic receptors for anions

We seek a theoretical method which is capable of predicting trends in the binding affinity of macrocyclic receptors for various anions in aqueous solution. Success has been achieved in this endeavor by employing semiempirical methodology to compute the energetics of certain exchange reactions whereby anions are exchanged between a macrocyclic receptor and a cluster of water molecules. The method is computationally tractable with workstation-class computing hardware and is applicable to a wide range of guest/host systems. Computations for several anion/receptor systems are reported.