Immobilization of methylviologen between well-ordered multilayers of manganese oxide during their electrochemical assembly

Methylviologen dications (MV2+) were immobilized between layers of manganese oxide during their electrochemical assembly by an anodic route in a homogeneous aqueous Mn2+ solution. This approach yielded a well-ordered multilayer film on a platinum substrate as a result of dense packing of planar MV2+ molecules to stabilize the layered framework. A grazing angle in-plane X-ray diffraction study revealed that the manganese oxide sheets and the molecular planes of inserted MV2+ ions are oriented parallel to the electrode surface. Cyclic voltammetry of the product film indicated an electron transfer from the underlying Pt substrate to inserted methylviologen ions through the manganese oxide sheets.     

Control of the stoichiometry in host-guest complexation by redox chemistry of guests: inclusion of methylviologen in cucurbit[8]uril

The binding stoichiometry of a host-guest complex can be effectively controlled by the redox chemistry of the guest: a 1:1 inclusion complex of methylviologen dication (MV2+) in cucurbit[8]uril (CB[8]) converts completely and reversibly to a 2:1 inclusion complex of cation radical (MV+.) in CB[8] upon the reduction of the guest.     

Large spontaneous polarization and clear hysteresis loop of a room-temperature hybrid ferroelectric based on mixed-halide [BiI3Cl2] polar chains and methylviologen dication

The search for hybrid organic-inorganic materials, which have the great advantage that they can be synthesized at moderate temperature (T < 200 °C), remains a great challenge in the field of ferroelectrics. Here, a room-temperature ferroelectric material with interesting characteristics, (MV)[BiI(3)Cl(2)] (MV(2+) = methylviologen), is reported. Its structure is based on polar inorganic chains resulting from a remarkable Cl/I segregation induced by methylviologen entities, which coincide with the fourfold polar axis of the tetragonal structure. Of great importance is that this room-temperature hybrid ferroelectric displays a clear electrical hysteresis loop with a large spontaneous polarization (>15 μC·cm(-2)).     

Effect of diffusion on the photoinduced reaction between a tetra-anionic porphyrin and methylviologen cation in methanol

The quenching of the fluorescence decay of electronically excited 5,10,15,20-tetraphenyl- 21H, 23H-porphinetetrasulfonate (TPPS (4-)*) in the presence of methylviologen cations (MV (2+)) was measured at various ionic strengths in methanol. Analysis of the fluorescence decay curves revealed strong evidence for the presence of a second fluorescent species over the entire range of ionic strength used in this work, which is attributed to solvent-separated ion pairs (TPPS (4-)-S-MV (2+)). Transient effects of the fluorescence decays were analyzed, and values for the effective reaction distance, R NH, and the diffusion coefficients, D, were obtained. Diffusion coefficients were independently measured for TPPS (4-) and MV (2+) using the Taylor dispersion method. The values for D obtained by the analysis of the transient effect were found to be smaller than those for the sum of the diffusion coefficients of TPPS (4-) and MV (2+) obtained by the Taylor dispersion method and a possible explanation for this result is given.     

Determination of oxidants with photoreduced methylviologen

Summary Determination of Oxidants with Photoreduced Methylviologen Optimal conditions for photogeneration of the reduced form of methylviologen are described in detail. The generation is done by photochemical reaction of the system 3,10-dimethyl-5-deazaisoalloxazine-methylviologen-electron donor (EDTA, oxalate or arginine). The methylviologen radical cation is suitable as a reductimetric titrant. A method has been developed for the determination of micromolar quantities of organic and inorganic substances byin situ photochemical generation of the reduced form of methylviologen. Spectrophotometric end-points can be utilized because of the intense blue colour of the titrant. Amperometric end-points can also be utilized. A precision of 1.5% can be obtained with both detection methods.     

The synthesis and properties of a methylviologen analogue

A novel derivative of methylviologen, prepared by transannular reaction of [2.2] (3,5) pyridinophane, shows large bathochromic shift in the electronic spectrum and nearly equal redox potential compared with methylviologen.     

Aggregation of amphiphilic pyranines in water: facile micelle formation in the presence of methylviologen

Four amphiphilic pyranines in which the acidic hydrogen of pyranine was replaced by an octyl, dodecyl, hexadecyl, and eicosyl group, POCn (n=8, 12, 16, and 20), were prepared, and their spectroscopic properties and aggregation behaviors in water were investigated. The critical micelle concentration (cmc) of the amphiphilic pyranines was found to be relatively large even in POC20 having a long hydrophobic alkyl chain (ca. 3x10(-3) M). 1H NMR studies revealed that POC16 and POC20 exist in the compact structure with the pyranine nucleus wrapped with a long methylene chain in water. As in the case of parent pyranine, the addition of methylviologen (MV2+) to an aqueous solution of POCn resulted in the absorption spectral change and efficient quenching of POCn fluorescence. In the case of POC8 and POC12, these spectral changes induced by the MV2+ addition were thoroughly explained in terms of the formation of the electrostatic complex POCn/MV2+ with a complexation constant of approximately 3x10(4) M(-1). On the other hand, an unexpectedly large dependence of the absorption spectral change, as well as fluorescence quenching, on the total concentration of MV2+ was observed in POC16 and POC20. The Stern-Volmer plot for quenching of the fluorescence of POC16 and POC20 gave a curve deviating largely upward from a straight line. The plot was successfully analyzed by the equation induced by assuming the aggregate formation of the complex POCn/MV2+, which revealed the considerably small cmc values of the complexes, 3.6x10(-7) and 3.6x10(-8) M for POC16/MV2+ and POC20/MV2+, respectively. Experimental evidence in support of the aggregate formation was obtained by 1H NMR and dynamic light scattering studies.     

A normal coordinate analysis of the vibrational modes of the three redox forms of methylviologen: Comparison with experimental results

A normal coordinate analysis of the three redox forms of methylviologen (MV) was accomplished using a simplified valence force field. The calculated band frequencies are compared with those observed experimentally. The plausibility of the assignments for the Raman A_g modes, as inferred from the normal coordinate analysis, is discussed. The assignments of several Raman A_g modes were checked by a comparison of the observed Raman spectra of viologens with different substituents, such as methyl group deuterated methyl viologen (DV), N-octyl-N′-methyl viologen (C₈MV), N-hexadecyl-N′-methyl viologen (C₁₆MV) and dibenzyl viologen (BV), with MV. The values of the root mean square (r.m.s.) amplitudes of vibrations between the bonded and the nonbonded atom pairs, and r.m.s. Cartesian displacements from the equilibrium geometry for MV²⁺ were computed. These data provide important insight with respect to the molecular geometry.     

Influence of surfactant vesicles and their polymerization on the complex formation between indoleacetate and methylviologen

 The association constant K between methylviologen MV and indoleacetate IA was decreased by the addition of cationic vesicles, and the K increased at high vesicle concen-trations. The influence of the polymerization of surfactants with different chain lengths on K was different. The concentration dependence of K was analyzed by a theory in terms of the partition coefficients of reactants between the bulk solvent phase and the local vesicle environment. The theoretical partition coefficients were determined graphically. The measured depen-dence of K on vesicle concentration was satisfactorily reproduced by the theory. When dimyrystyldiallylammonium bromide (DMAB) was added to the complex, the polymerization of the surfactant increased the partition coefficients of IA and the complex but decreased that of MV. However, the polymerization of dicetyldiallylammonium bromide (DCAB) showed the reverse tendency. The influence of polymerization on K or the partition coefficient was discussed in terms of the difference in the polymerization mechanism due to the differences in the distance between the neighboring nonpolymerized surfactant molecules and the polymerization induced change in that distance. Received: 10 May 1996 Accepted: 27 August 1996     

Crystal structures and spectroscopic properties of polycyano-polycadmate host clathrates including a CT complex guest of methylviologen dication and aromatic donor

A series of polycyano-polycadmate (PCPC) host clathrates including a CT complex of methylviologen dication (MV2+) and an aromatic donor as a guest were synthesized, and their crystal structures and spectroscopic properties were investigated. The PCPC host has a framework structure built with Cd2+ ions as coordination centres and cyanides as bridging ligands. This framework host has negative charge and includes a cationic guest together with an ordinary neutral guest. MV2+, which is a strong acceptor, was included as a cationic guest and an aromatic compound, which works as a donor, was included as a neutral guest. Crystal structures of seven clathrates, whose neutral guests were o-cresol, m-cresol, p-cresol, 1-methylnaphthalene, 1,2,4-trimethoxybenzene, pyrrole and aniline, were determined by single crystal X-ray diffraction methods. In all cases MV2+ and the neutral guest formed a CT complex with a face to face stacking structure and were included as a CT complex guest. However, depending on each clathrate the ratio of aromatic donor to MV2+ was different and several variations were found in their PCPC host structures. The clathrates had their own colour depending on their neutral guest. The plot of the CT transition energies estimated from optical CT bands against the ionization potentials of the neutral guests satisfied a linear relationship predicted by Mulliken theory. However, the CT transition energies observed in the clathrates showed a shift to lower energy by ca. 0.6 eV compared with those observed in corresponding acetonitrile solutions.     

Strong electron-acceptor methylviologen dications confined in a 2D inorganic host: synthesis, structural characterization, charge transport and electrochemical properties of (MV)(0.25)V(2)O(5).

The reaction of methylviologen iodide with crystalline V2O5 in the molar ratio of 1 to 3.8 at 100 degrees C in water led to the formation of (MV)0.25V2O5 in quantitative yield. The structure of this organic-inorganic multilayered hybrid compound was determined by single-crystal X-ray crystallography. Strong van der Waals interactions were found between the electron-deficient aromatic organic molecules and the inorganic layers. In the solid state, the compound is a semiconductor due to small polaron hopping and shows novel reversible alkali-ion intercalation/deintercalation via electrochemistry.     

Strong electron-accepting methylviologen dication confined in magnetic hosts: synthesis, structural characterization, charge-transfer and magnetic properties of {(MV)2[Ni(SCN)5].Cl.2H2O}n and {(MV)[m(N3)2(SCN)2]}n (M=Mn, Co)

Three hybrid host-guest compounds {(MV)2[Ni(SCN)5].Cl.2H2O}n (1), {(MV)[Mn(N3)2(SCN)2]}n (2) and {(MV)[Co(N3)2(SCN)2}n (3) (where MV2+ = methylviologen dication) have been obtained by self-assembly methods and characterized by X-ray crystallography, spectral methods and magnetic measurements. Compound 1 shows a quasi-two-dimensional structure which is formed by novel single thiocyanate-bridged Ni(II) chains connected through S...S interactions. Compounds 2 and 3 are isostructural, containing single micro(1,3)-azide bridged Mn(II)/Co(II) square layers. MV2+, as a strong electron-acceptor and a template, is embedded between the anionic layers in all three compounds. The charge-transfer (CT) interactions between MV2+ and the anionic hosts have been revealed by structural analysis and UV-vis diffuse reflection spectroscopy. The magnetic studies of the compounds show antiferromagnetic interactions between adjacent metal ions (J = -34.52(7) cm(-1) for 1, J = -3.90(2) cm(-1) for 2 and J = -10.96(6) cm(-1) for 3).     

Effective luminescence quenching of tris(2,2-bipyridine)ruthenium(II) by methylviologen on clay by the aid of poly(vinylpyrrolidone)

Electron-transfer quenching of tris(2,2-bipyridine)ruthenium(II) by methylviologen in an aqueous suspension of clay in the presence of poly(vinylpyrrolidone) was investigated. The quenching behavior of the excited tris(2,2-bipyridine)ruthenium(II) on clay by the coadsorbed methylviologen indicated the homogeneous distribution of the adsorbed dyes. The quenching rate was high when the clay with larger particle size was used as the host. The adsorption of poly(vinylpyrrolidone) on clay resulted in the coadsorption of the tris(2,2-bipyridine)ruthenium(II) and methylviologen without segregation.     

Ruthenium-phenothiazine electron transfer dyad with a photoswitchable dithienylethene bridge: flash-quench studies with methylviologen

A molecular ensemble composed of a phenothiazine (PTZ) electron donor, a photoisomerizable dithienylethene (DTE) bridge, and a Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) electron acceptor was synthesized and investigated by optical spectroscopic and electrochemical means. Our initial intention was to perform flash-quench transient absorption studies in which the Ru(bpy)(3)(2+) unit is excited selectively ("flash") and its (3)MLCT excited state is quenched oxidatively ("quench") by excess methylviologen prior to intramolecular electron transfer from phenothiazine to Ru(III) across the dithienylethene bridge. However, after selective Ru(bpy)(3)(2+1)MLCT excitation of the dyad with the DTE bridge in its open form, (1)MLCT → (3)MLCT intersystem crossing on the metal complex is followed by triplet-triplet energy transfer to a (3)π-π* state localized on the DTE unit. This energy transfer process is faster than bimolecular oxidative quenching with methylviologen at the ruthenium site (Ru(III) is not observed); only the triplet-excited DTE then undergoes rapid (10 ns, instrumentally limited) bimolecular electron transfer with methylviologen. Subsequently, there is intramolecular electron transfer with PTZ. The time constant for formation of the phenothiazine radical cation via intramolecular electron transfer occurring over two p-xylene units is 41 ns. When the DTE bridge is photoisomerized to the closed form, PTZ(+) cannot be observed any more. Irrespective of the wavelength at which the closed isomer is irradiated, most of the excitation energy appears to be funneled rapidly into a DTE-localized singlet excited state from which photoisomerization to the open form occurs within picoseconds.     

Inclusion of methylviologen dication in a cadmium tetracyanoplatinate host clathrate showing photochromism and photoluminescence modulation

A cadmium tetracyanoplatinate host clathrate, (MV)[Cd₂{Pt(CN)₄}₃]?2(H₂O) (1), including a methylviologen dication (MV²⁺) was synthesized, and the crystal structures, photochromic and photoluminescence properties were investigated. In 1, the alternatively parallel stacking between the MV²⁺ dications as electron acceptors in the channels and the electron donors [Pt1(CN)₄]^2– units in the host frameworks give a unique donor-acceptor (DA) system. Under UV irradiation, the electron transfer between MV²⁺ and [Pt(CN)₄]^2– ions generates MV^·+ radicals with a photochromic behavior from pale-yellow to blue. This process occurs through single-crystal-to-single-crystal (SCSC) transformation and obvious structure variation of viologen cations is successfully observed. Moreover, the spectral overlap between the emission bands of 1 and the absorption around 623 nm for the MV^·+ radicals leads to a modulation of the photoluminescence.     

Redox reactions in micellar systems Communication 4. Eosin-photosensitized reduction of methylviologen

Conclusions Photosensitized reduction of methylviologen by an electron donor (EDTA) in micellar solutions can model photosystem I of plants with structure formation of reagents and transfer of excitation energy before the step of occurrence of a redox reaction in the active center.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1293–1296, June, 1985.     

Cucurbit[8]uril induced heterodimerization of methylviologen and naphthalene functionalized proteins

Cucurbit[8]uril is a supramolecular inducer of protein heterodimerization for proteins appended with methylviologen and naphthalene host elements. Two sets of fluorescent protein pairs, which visualize the specific protein assembly process, enabled the interplay of the supramolecular elements with the proteins to be established.     

Charge transfer complex between methylviologen and ferrocyanide

Charge transfer complex between methylviologen and ferrocyanide has been studied spectrophotometrically at different temperatures. From the thermodynamic association constants (320 ± 30 M⁻¹, 380 ± 30 M⁻¹ and 460 ± 40 M⁻¹ at 15, 25 and 30°C respectively), the enthalpy of formation, ΔH° (− 3.4 ± 1.5 kcal/mole), and the related entropy change, ΔS°(0.4 ± 5 e.u), have been calculated. The average extinction values of coefficients are 69±6 M⁻¹ cm⁻¹, 70±4 M⁻¹ cm⁻¹ and 72±5 M⁻¹ cm⁻¹ at 15, 25 and 35°C respectively.     

光敏氧化还原反应 VI: 卟啉光敏还原甲基紫精的溶剂效应

本文报道水溶性卟啉在DMSO-H2O混合体系中光敏还原甲基紫精的最新结果. 本研究包括三个敏化剂: ZnTPRS、二羟基锡(IV)meso-四(p-磺酸苯基)卟啉(Sn TPPS)和ZnTMPyP. 在0,20,40,60和80%DMSO水溶液中比较了敏化剂光敏还原甲基紫精的能力, 观察到量子产率随DMSO的比例而增长.     

Quenching of photo-excited state of copolymer pendant Ru(bpy) complexes with methylviologen

Copolymer pendant tris(2,2′-bipyridine)ruthenium(II) complexes were prepared from the copolymers of 4-methyl-4′-vinyl-2,2′-bipyridine with styrene, acrylic acid, methyl methacrylate, hydroxyethyl methacrylate, acrylonitrile, N-vinylpyrrolidone, 4-vinylpyridine, and quaternized 4-vinylpyridine. The quenching of the photo-excited state of the polymer complexes by methylviologen was studied. Pendant anionic groups such as acrylate enhanced remarkably the quenching of the cationic sensitizer by the cationic substrate, however, pendant cationic groups such as quaternized pyridine did not affect the reaction. The polymer chain showed generally retarding effect on the quenching reaction.