A surfactant-encapsulated polyoxometalate complex towards a thermotropic liquid crystal

A novel surfactant-encapsulated terbium-substituted heteropolyoxotungstate complex [L1]13[Tb(SiW11O39)2].30H2O (SEC-1) bearing mesomorphous groups was successfully prepared by the ionic self-assembling route, exhibiting characteristic thermotropic liquid-crystalline behavior.     

Thermotropic mesomorphic behavior of surfactant-encapsulated polyoxometalate hybrids

We investigate in detail novel organic-inorganic hybrid liquid crystalline materials, the complexes of surfactant-encapsulated polyoxometalate clusters (SECs), using thermal, X-ray diffraction, and FT-IR spectroscopic analyses. The differential scanning calorimetry measurements reveal four phase transitions under heating processes. We employ FT-IR spectroscopy to understand these phase behaviors. On the basis of vibration spectral assignments, the evidence suggests that the first two phase transitions are associated with the increase of gauche conformers and the disruption of alkyl chains packing in the heating run; the third phase transition is due to the full conformational disorder of alkyl chains covered on the polyoxometalates (PMs); no significant C-H stretching or wagging vibrations are observed with the fourth transition. We find that the fourth endothermic peak is sensitive to the charges of the PMs, and the transition temperature decreases from 185, 177, to 164 degrees C with decreasing PM charges from 13, 11, to 9, respectively. Interestingly, the temperatures of the first three phase transitions of SECs are essentially independent of the PM charges.     

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.     

Self-organized microporous structures based on surfactant-encapsulated polyoxometalate complexes

Self-organized microporous structures based on a series of surfactant-encapsulated polyoxometalate complexes (SECs) have been prepared by using ordered condensed droplets as a template. Among these structures, ordered honeycomb structures were obtained and characterized in detail by taking (DODA)(12)H[Eu(SiW(11)O(39))2] (SEC-1) as an example. Optical microscope, atomic force microscopic, and scanning electron microscopic measurements confirmed the formation of three-dimensional microporous structure, in which the top surface shows a highly ordered honeycomb structure. As compared to common solvent-casting films, the corresponding honeycomb films are more hydrophobic and possess more ordered lamellar structures. Both the wettability and the size of SECs exert significant influence on the formation of microporous structures. The proper hydrophobicity of SECs was proposed to be an essential factor for the formation of honeycomb films, and large-sized SECs are favorable for the fabrication of highly ordered honeycomb structures. The conditions for the formation of different surface morphologies have been discussed in terms of the contact angle of SECs at the interface between water and chloroform, and a contact angle slightly greater than 90 degrees is found to be a prerequisite for the formation of honeycomb structures. The results reported in this paper not only help to further comprehend the mechanism of the formation of honeycomb structures, but also provide some guidance for the design of ordered microporous films based on organic/inorganic hybrid materials, exemplified by the organic/nanoparticle complexes.     

Hierarchical self-assembly of surfactant-encapsulated and organically grafted polyoxometalate complexes

A series of surfactant-encapsulated and organically grafted polyoxometalates (SEOPs) were prepared through a co-precipitation procedure. Through a rational selection of the molecular components in the structure of the complex, SEOP complexes self-assemble into ordered aggregates with two different hierarchical self-assembled structures in an organic solvent mixture of dichloromethane and methanol in different volume ratios. FTIR, (1)H NMR, and X-ray photoelectron spectroscopy were used to characterize the self-assembly process and the involved driving forces. In a weakly polar solvent, SEOPs aggregated into fibers with a lamellar structure. When the solvent polarity was increased, SEOPs formed ribbonlike aggregates with a tetragonal structure. The change of the hierarchical self-assembled structure was deduced in regard to the arrangement of alkyl chains, electrostatic interactions, and hydrogen bonding between the pyridyl groups and terminal oxygen atoms of the polyoxometalates. The ribbonlike aggregates exhibit birefringence due to the ordered arrangement of SEOPs in the microstructure.     

Isolated and linear arrays of surfactant-encapsulated polyoxometalate clusters on graphite

We report on the self-assembly of several surfactant-encapsulated clusters (SECs) on the basal plane of graphite consisting of the doughnut-shaped tungstophosphate anion [Na(H2O)P5W30O110] covered by a hydrophobic shell of surfactants. Well-ordered rodlike structures are observed using scanning force microscopy. No such ordering is observed if the surfactant methyltrioctadecylammonium is used for encapsulation, suggesting that the density of alkyl chains around the polyoxometalate cluster is an important factor in determining the order of SEC assemblies on graphite. Coadsorption of tetratetracontane (n-C44H90) and (DODA)14[Na(H2O)P5W30O110] results in single, isolated SECs on a buffer layer of tetratetracontane, as determined by scanning tunneling microscopy.     

In situ photopolymerization and photophysical properties of a surfactant-encapsulated polyoxometalate in casting film

In this paper, we constructed an ordered self-organized film possessing a well-defined layered structure by using a polymerizable surfactant-encapsulated polyoxometalloeuropate, (DMDA)9EuW10O36 (DMDA: dodecyl(11-methacryloyloxyundecyl)dimethylammonium bromide). The in situ polymerization of the film through UV irradiation was investigated by using 1H NMR and FTIR spectra, and X-ray diffraction. The results show that 68% of the monomers that connect to the complex in the film have been polymerized at the utmost. In contrast to the virgin layered structure of the casting film which possesses a layer spacing of 2.7 nm, the layer thickness increases to about 3.3 nm after the in situ polymerization. The lifetime and the quantum yield of the polyoxometalate in the casting film were found to increase due to the change of the layered structure after in situ polymerization. Thus, the present results provide an effective way to tune the photophysical properties of the film through alteration of the layered structure. In the meantime, the stability of the casting film in the alkaline solution was improved after in situ polymerization.     

Self-assembled monolayers of CH3COS- terminated surfactant-encapsulated polyoxometalate complexes

Self-assembled monolayers (SAMs) on gold surfaces based on three kinds of acetylthio-surfactant-encapsulated polyoxometalate clusters (thio-SECs) terminated with multiple CH(3)COS- groups, (NC(26)H(55)S(CO)CH(3))(6)H(2)[Co(H(2)O)CoW(11)O(39)], (NC(26)H(55)S(CO)CH(3))(13)H(3)[Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)], and (NC(26)H(55)S(CO)CH(3))(13)[Fe(4)(H(2)O)(2)(P(2)W(15)O(56))(2)]Br, have been prepared, which is representative of a general methodology to fabricate polyoxometalate-based SAMs. Thio-SECs self-assembled into monolayers on gold surfaces through the hydrolysis of CH(3)COS- groups and the subsequent formation of S-Au bonds, which was confirmed by grazing angle infrared spectroscopy, X-ray photoelectron spectroscopy, and ellipsometric and scanning tunneling microscopy (STM) measurements. Furthermore, the SAMs of the thio-SECs possess closely packed structures, and the local short-range order is clearly observed in the magnified STM image. We have also investigated the electrochemical behavior of SAMs of thio-SECs by cyclic voltammetry in detail, and the redox potential of the original polyoxometalates has been well retained. The electrochemical signals of the SAMs are very weak because of the small moiety of thio-SECs that are electrochemically accessible in the cyclic voltammetry experiments. The polyoxometalate-modified electrodes that we prepared are not only highly ordered in the local short range but also stable in electrochemical cycling because of the multiple S-Au bonds of thio-SECs on the gold substrates that aid in the construction of functional materials such as electrochemical and electrocatalytic devices.     

Stable photochromism and controllable reduction properties of surfactant-encapsulated polyoxometalate/silica hybrid films

In this paper, we present a novel strategy for fabricating polyoxometalate (POM)-based photochromic silica hybrid films. To combine metal nanoparticles (NPs) into the POMs embedded silica matrix, furthermore, we realized the controllable in situ synthesis of metal NPs in the film by utilizing the reduction property of POMs existing in the reduced state. Through electrostatic encapsulation with hydroxyl-terminated surfactants, the POMs with good redox property can be covalently grafted onto a silica matrix by means of a sol-gel approach, and stable silica sol-gel thin films containing surfactant-encapsulated POMs can be obtained. The functional hybrid film exhibits both the transparent and easily processible properties of silica matrix and the stable and reversible photochromism of POMs. In addition, well-dispersed POMs in a hydrophobic microenvironment within the hybrid film can be used as reductants for the in situ synthesis of metal NPs. More significantly, the size and location of NPs can be tuned by controlling the adsorption time of metal ions and mask blocking the surface. The hybrid film containing both POMs and metal NPs with patterned morphology can be obtained, which has potential applications in optical display, memory, catalysis, microelectronic devices and antibacterial materials.     

The first structural and spectroscopic characterization of a neptunyl polyoxometalate complex

The reaction between PW9O349- and NpO2+ has yielded the first structurally characterized neptunyl(V) polyoxometalate complex, [Na2(NpO2)2(A-PW9O34)2]14-. This complex is isostructural with the uranyl(VI) analogue, and there is also spectroscopic evidence for its existence in solution. The complex is readily extracted into toluene, and this may have significance in the sequestering and/or separation of the neptunyl ion in terms of nuclear waste management.     

Luminescent thermo- and photocurable silicones doped with a europium complex

Two europium ??-diketonates containing tris(trimethylsiloxysilylpropylamide) group in the ligand molecule were obtained by the reaction of the corresponding triethoxysilyl derivatives with trimethylsilanol. The siloxane groups provide solubility of the complexes in liquid silicone compositions, which is sufficient for obtaining luminescent flexible polysiloxane films doped with the europium complex.     

A novel organic-inorganic hybrid based on a dinuclear copper complex supported on a keggin polyoxometalate

The autoassembly process of copper-oxalate dimers and Keggin type polyoxometalates leads to the first example of a new family of organic-inorganic hybrids, K(14)[(Cu(2)(bpy)(2)(mu-ox))(SiW(11)O(39)Cu(H(2)O))](2)[SiW(11)O(39)Cu(H(2)O)]. approximately 55H(2)O. This compound crystallizes in the monoclinic space group C2/m, a = 37.932(6) A, b = 21.303(3) A, c = 12.546(2) A, beta = 106.16(1) degrees, Z = 2. The crystal structure reveals the presence of a polymeric hybrid built up of alternating dimer and polyoxometalate entities.     

Theoretical study of the exchange coupling interactions in a polyoxometalate Fe9W12 complex

Theoretical methods based on density functional theory have been employed to analyze the exchange interactions in a Fe₉W₁₂ polyoxometalate complex. The calculated values of the seven exchange coupling constants required by the molecular structure agree well with those reported previously for other Fe^III polynuclear complexes and give an S = 15/2 single determinant ground state, with a first excited state that has S = 5/2.     

Tandem pinacol coupling-rearrangement of aromatic aldehydes with hydrogen catalyzed by a combination of a platinum complex and a polyoxometalate

Together with a strongly oxidizing polyoxometalate, H(5)PV(2)Mo(10)O(40), Pt(II)(N-(2,6-diisopropylphenyl)pyrazin-2-ylmethanimine)Cl2 forms a combined catalyst that was active in the tandem pinacol coupling-rearrangement of aryl aldehydes to give mostly the corresponding diarylacetaldehyde in high yields using molecular hydrogen as the reducing agent.     

Investigation on solvent casting films of surfactant-encapsulated clusters

The surfactant-encapsulated cluster (SEC) composed of a hydrophobic dimethyl dioctadecyl ammonium (DODA) shell and an encapsulated hydrophilic polyoxoanion core can form casting films. The structure of the casting film is influenced by evaporation rates of organic solvent. When the casting films are prepared by slow evaporation of chloroform, the alkyl chains are considered to possess a partial interdigitation, and the interdigitated length is 1.6 nm. The casting film structure is characterized by scanning force microscopy (SFM), Fourier transformation infrared (FT-IR), wide-angle X-ray diffraction, and differential scanning calorimetry (DSC).     

Synthesis and characterization of a new dimeric polyoxometalate based on Anderson-type polyoxoanions and a trinuclear lanthanide coordination complex

An unusual compound, H₅[(C₆NO₂H₄)₄(H₂O)₁₅Nd₃][IMo₆O₂₄]₂·13.5H₂O (1) has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and single crystal X-ray diffraction. Compound 1 consists of two [IMo₆O₂₄]^5? units joined by a trinuclear neodymium-pyridine-4-carboxylic acid complex, resulting in a dimeric polyoxometalate, which further interact via weak intermolecular interactions to form a three-dimensional supramolecular framework with channels. To the best of our knowledge, no analogous dimeric polyoxometalate structure composed of an Anderson-type polyoxometalate has been reported in the literature.     

The fundamental Fuzzy logic operators and some complex boolean logic circuits implemented by the chromogenism of a spirooxazine

1,3-Dihydro-1,3,3-trimethyl-8'-nitro-spiro[2H-indole-2,3'-[3H]naphth[2,1-b][1,4]oxazine] (SpO) is a photochromic, acidichromic and metallochromic compound. Its chromogenic properties are characterized in acetonitrile, at room temperature. They are exploited to process both boolean and Fuzzy logic. By using HClO(4), AlCl(3) and Cu(ClO(4))(2) as chemical inputs, UV radiation as power supply, and the absorbance at specific wavelengths in the visible as optical output, SpO results in a five-states molecular switch whereby some complex boolean logic circuits are implemented. If the chemical inputs are varied in an analog manner, the solution of SpO assumes an infinite number of colours. Therefore, by choosing the RGB colour coordinates as optical outputs, the fundamental operators of the "infinite-valued" Fuzzy logic are implemented. Particularly, two Fuzzy logic systems are built upon a new defuzzification procedure imitating the way humans perceive colours.     

A switchable macrocycle-clip complex that functions as a NOR logic gate

We have synthesized a new molecular switch-based on a macrocycle-clip complex-whose switching behavior not only can be controlled through the use of either K+-[2,2,2]cryptand or NH4+-Et3N systems but also provides color changes that are visible to the naked eye; consequently, this system operates as a two-input NOR functioning molecular logic gate.