Contrasting Photoelectrochemical Behaviour Of Two Isomeric Supramolecular Dyes Based On Meso-tetra(pyridyl)porphyrin Incorporating Four (μ3-oxo)- Triruthenium(iii) Clusters

A saddle shaped tetracluster porphyrin species containing four [Ru 3O(OAc)6(py)2]+ clusters coordinated to the N-pyridyl atoms of 5,10,15,20-tetra(3-pyridyl)porphyrin, H 2(3-TCPyP), has been investigated in comparison with the planar tetra(4-pyridyl)porphyrin analogue H2(4-TCPyP). The steric effects from the bulky peripheral complexes play a critical role in the H 2(3-TCPyP) species, determining a non-planar configuration around the porphyrin centre and precluding any significant π-electronic coupling, in contrast with the less hindered H2(4-TCPyP) species. Both systems exhibit a photoelectrochemical response in the presence of nanocrystalline TiO2 films, involving the porphyrin excitation around 450 nm. However, only in the H2(4-TCPyP) case do the cluster moieties also contribute to the photoinduced electron injection process at 670 nm, reflecting the relevance of the electronic coupling between the porphyrin centre and the peripheral complexes. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.32711671174Araki, K., Toma, H.E., Supramolecular porphyrins as electrocatalysts, in (2006) N-4 Macrocyclic Metal Complexes, Ed., , J. H. Zagal, F. Bedioui and J.-P. Dodelet, Springer, pp. 255-302Toma, H.E., Araki, K., (2000) Coord. Chem. Rev., 196, p. 307Latos-Grazynski, L., Rachlewicz, K., Wojaczynski, J., (1999) Coord. Chem. Rev., 192, p. 109Imamura, T., Fukushima, K., (2000) Coord. Chem. Rev., 198, p. 133Sanders In, J.K.M., (2000) The Porphyrin Handbook, Ed., , K. M. Kadish, et al., Academic Press, New YorkChambron, J.C., Heitz, V., Sauvage In, J.P., (2000) The Porphyrin Handbook, Ed., , K. M. 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Electrocatalytic Oxidation Of Methanol By The [ru3o(oac) 6(py)2(ch3oh)]3+ Cluster: Improving The Metal-ligand Electron Transfer By Accessing The Higher Oxidation States Of A Multicentered System

The [Ru3O(Ac)6(py)2(CH3OH)] + cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3 III,II,II/Ru3 III,III,II/ Ru3 III,III,III/Ru3 IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two Ru IV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.331020462050Viertler, H., Gruber, J., Pardini, V.L., (2001) Organic Electrochemistry, p. 621. , Lund, H.Hammerich, O., eds.Marcel Dekker: New York, chap. 17Araki, K., Toma, H.E., (2006) N-4 Macrocyclic Metal Complexes, p. 255. , Zagal, J. H.Bedioui, F.Dodelet, J.-P.Springer: New York, chap. 6Araki, K., Dovidauskas, S., Winnischofer, H., Alexiou, A.D.P., Toma, H.E., (2001) J. Electroanal. Chem., 498, p. 152Dovidauskas, S., Toma, H.E., Araki, K., Sacco, H.C., Iamamoto, Y., (2000) Inorg. Chim. Acta, 305, p. 208Toma, H.E., Araki, K., (2009) Progr. Inorg. Chem., 56, p. 379Kuwabara, I.H., Comninos, F.C.M., Pardini, V.L., Viertler, H., Toma, H.E., (1994) Electrochim. Acta, 39, p. 2401Nunes, G.S., Alexiou, A.D.P., Araki, K., Formiga, A.L.B., Rocha, R.C., Toma, H.E., (2006) Eur. J. Inorg. Chem., p. 1487Nunes, G.S., Alexiou, A.D.P., Toma, H.E., (2008) J. Catal., 260, p. 188Alexiou, A.D.P., Dovidauskas, S., Toma, H.E., (2000) Quim. Nova, 23, p. 785Toma, H.E., Araki, K., Alexiou, A.D.P., Nikolaou, S., Dovidauskas, S., (2001) Coord. Chem. Rev., 219-221, p. 187Davis, S., Drago, R.S., (1988) Inorg. Chem., 27, p. 4759Bilgrien, C., Davis, S., Drago, R.S., (1987) J. Am. Chem. Soc., 109, p. 3786Sieben, J.M., Duarte, M.M.E., Mayer, C.E., (2010) Chem Cat. Chem, 2, p. 182Raoof, J.B., Golikan, A.N., Baghayeri, M., (2010) J. Solid State Electrochem., 14, p. 817Raoof, J.B., Karimi, M.A., Hosseini, S.R., Mangelizadeh, S., (2010) J. Electroanal. Chem., 638, p. 33El-Deab, M.S., (2009) Int. J. Electrochem. Sci., 4, p. 1329Zheng, L., Song, J.F., (2010) J. Solid State Electrochem., 14, p. 43Wu, B.H., Hu, D., Kuang, Y.J., Liu, B., Zhang, X.H., Chen, J.H., (2009) Angew. Chem., Int. Ed., 48, p. 4751Suffredini, H.B., Salazar-Banda, G.R., Avaca, L.A., (2009) J. Sol-Gel Sci. Technol., 49, p. 131Balasubramanian, A., Karthikeyan, N., Giridhar, V.V., (2008) J. Power Sources, 185, p. 670Zhao, H.B., Li, L., Yang, J., Zhang, Y.M., (2008) Electrochem. Commun., 10, p. 1527Zhang, D., Ding, Y., Gao, W., Chen, H.Y., Xia, X.H., (2008) J. Nanosci. Nanotechnol., 8, p. 979Sawyer, D.T., Roberts, J.L., (1974) Experimental Electrochemistry for Chemists, , Wiley: New YorkBaumann, J.A., Salmon, D.J., Wilson, S.T., Meyer, T.J., Hatfield, W.E., (1978) Inorg. Chem., 17, p. 3342Allinger, N.L., (1977) J. Am. Chem. Soc., 99, p. 8127Zerner, M.C., Loew, G.H., Kirchner, R.F., Mueller-Westerhoff, U.T., (1980) J. Am. Chem. Soc., 102, p. 589Formiga, A.L.B., Nogueira, A.F., Araki, K., Toma, H.E., (2008) New J. Chem., 32, p. 1167Longuet-Higgins, H., Pople, J.A., (1955) Proc. Phys. Soc., 68, p. 591Latimer, W.M., (1952) The Oxidation States of the Elements and Their Potentials in Aqueous Solutions, , Prentice-Hall: Englewood Cliffs, 2nd edNicholson, R.S., Shain, I., (1964) Anal. Chem., 36, p. 706Sundholm, G., (1971) Acta Chem. Scand., 25, p. 3188Sundholm, G., (1971) J. Electroanal. Chem., 31, p. 265Nash, T., (1953) Biochemistry, 55, p. 41

Solar parameters for modeling interplanetary background

The goal of the Fully Online Datacenter of Ultraviolet Emissions (FONDUE) Working Team of the International Space Science Institute in Bern, Switzerland, was to establish a common calibration of various UV and EUV heliospheric observations, both spectroscopic and photometric. Realization of this goal required an up-to-date model of spatial distribution of neutral interstellar hydrogen in the heliosphere, and to that end, a credible model of the radiation pressure and ionization processes was needed. This chapter describes the solar factors shaping the distribution of neutral interstellar H in the heliosphere. Presented are the solar Lyman-alpha flux and the solar Lyman-alpha resonant radiation pressure force acting on neutral H atoms in the heliosphere, solar EUV radiation and the photoionization of heliospheric hydrogen, and their evolution in time and the still hypothetical variation with heliolatitude. Further, solar wind and its evolution with solar activity is presented in the context of the charge exchange ionization of heliospheric hydrogen, and in the context of dynamic pressure variations. Also the electron ionization and its variation with time, heliolatitude, and solar distance is presented. After a review of all of those topics, we present an interim model of solar wind and the other solar factors based on up-to-date in situ and remote sensing observations of solar wind. Results of this effort will further be utilised to improve on the model of solar wind evolution, which will be an invaluable asset in all heliospheric measurements, including, among others, the observations of Energetic Neutral Atoms by the Interstellar Boundary Explorer (IBEX).Comment: Chapter 2 in the planned "Cross-Calibration of Past and Present Far UV Spectra of Solar System Objects and the Heliosphere", ISSI Scientific Report No 12, ed. R.M. Bonnet, E. Quemerais, M. Snow, Springe

Synthesis, Spectroscopy, Tandem Mass Spectrometry, And Electrochemistry Of The Linearly Bridged μ-{trans-1,4-bis[2-(4-pyridyl)ethenyl]-benzene}-{ru 3o(ch3coo)6(py)2}2 Cluster

The novel polynuclear [{Ru3O(CH3COO) 6(py)2}2(BPEB)](PF6)2 species containing the linear bridging trans-1,4-bis[2-(4-pyridyl)ethenyl]- benzene ligand (BPEB) was synthesized and its structural characterization carried out by means of positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry, as well as by 1H NMR spectroscopy. The doubly charged cation [{Ru3O(CH3COO)6(py) 2}2(BPEB)]2+ was detected in the ESI-MS mass spectrum as a multiple-component isotopomeric ionic cluster centered at m/z 974, which ion abundance and m/z distribution matched perfectly the isotopic pattern calculated for this multiple isotope Ru3-containing ion. The tandem mass spectrum of [{Ru3O(CH3COO)6(py) 2}2(BPEB)]2+ provided a structural diagnostic dissociation behavior, on the basis of the characteristic charge splitting and sequential ligand loss steps. The cyclic voltammograms of the complex exhibited a quasi-reversible multistep redox behavior, displaying three waves at 1.14, 0.08, and -1.21 V ascribed to the [Ru3O]2+/1+/0/1- processes and two waves at -1.56 and -1.78 V ascribed to the BPEB 0/1-/2- redox processes which are also observed in the free ligand, at -1.48 and 1.61 V, respectively. In spite of the conducting nature of the bridging ligand, the electrochemical and spectroelectrochemical results indicated a weak electronic coupling between the triangular cluster centers. © 2004 Published by Elsevier B.V.357822532260Toma, H.E., Araki, K., Alexiou, A.D.P., Nikolaou, S., Dovidauskas, S., (2001) Coord. Chem. Rev., 187, p. 219Alexiou, A.D.P., Dovidauskas, S., Toma, H.E., (2000) Quim. Nova, 23, p. 785Busleva, T.M., Red'Kina, S.N., Rudnitskaya, O.V., (1999) Russ. J. Coord. Chem., 25, p. 3Rocha, R.C., Toma, H.E., (2002) Quim. Nova, 25, p. 624Toma, H.E., Cunha, C.J., Cipriano, C., (1988) Inorg. Chim. Acta, 154, p. 63Alexiou, A.D.P., Toma, H.E., (1993) J. Chem. Res. (S), p. 464Toma, H.E., Cipriano, C., (1989) J. Electroanal. Chem., 263, p. 313Toma, H.E., Matsumoto, F., Cipriano, C., (1993) J. Electroanal. Chem., 346, p. 261Ward, M.D., (1995) Chem. Soc. Rev., p. 121Das, A., Maher, J.P., McCleverty, J.A., Badiola, J.A.N., Ward, M.D., (1993) J. Chem. Soc., Dalton Trans., p. 681(1997) Electrospray Ionization Mass Spectrometry, , R.B. Cole. New York: WileyColton, R., D'Agostinho, A., Traeger, J.C., (1995) Mass Spectrom. Rev., 14, p. 79Griep-Raming, J., Meyer, S., Bruhn, T., Metzger, J.O., (2002) Angew. Chem. Int. Ed., 41, p. 2738Arakawa, R., Tachiyashiki, S., Matsuo, T., (1995) Anal. Chem., 67, p. 4133Eberlin, M.N., Meurer, E., Santos, L.S., Pilli, R.A., (2003) Org. Lett., 5, p. 1391Plattner, D.A., (2001) Int. J. Mass Spectrom., 207, p. 125Baumann, J.A., Salmon, D.J., Wilson, S.T., Meyer, T.J., Hatfield, W.E., (1978) Inorg. Chem., 17, p. 3342Heck, R.F., (1981) Org. React., 27, p. 345Amoroso, A.J., Thompson, A.M.W.C., Maher, J.P., McCleverty, J.A., Ward, M.D., (1995) Inorg. Chem., 34, p. 4828Toma, H.E., Alexiou, A.D.P., (1995) J. Chem. Res. (S), p. 134Toma, H.E., Alexiou, A.D.P., Nikolaou, S., Dovidauskas, S., (1999) Magn. Reson. Chem., 37, p. 322Alexiou, A.D.P., Toma, H.E., (1997) J. Chem. Res. (S), p. 338Nikolaou, S., Uemi, M., Toma, H.E., (2001) Spectrosc. Lett., 34, p. 267Bertini, I., Luchinat, C., (1996) Coord. Chem. Rev., 150, p. 1Silverstein, R.M., Bassler, G.C., Morrill, T.C., (1991) Spectrometric Identification of Organic Compounds, , New York: Wiley. p. 221Baumann, J.A., Salmon, D.J., Wilson, S.T., Meyer, T.J., (1979) Inorg. Chem., 18, p. 2472Toma, H.E., Cunha, C.J., (1989) Can. J. Chem., 67, p. 163

Synthesis And Characterization Of The [ru3o(ch 3coo)6(py)2(bpe)ru(bpy)2cl](pf 6)2 Dimer

The polymetallic [Ru3O(CH3COO)6(py) 2(BPE)Ru(bpy)2Cl](PF6)2 complex (bpy = 2,2'-bipyridine, BPE = trans-1,2-bis(4-pyridil)ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru3O] moiety with a [Ru(bpy)2(BPE)Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry. The [Ru3O(CH3COO)6(py) 2(BPE)Ru(bpy)2Cl]2+ doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)2(BPE)] charge-transfer bands and to the [Ru 3O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at -1.07 V, 0.13 V, 1.17 V, 2.91 V and -1.29 V (vs SHE) assigned to the [Ru3O]-1/0/+1/+2/+3 and to the bpy 0/-1 redox processes; also a wave is observed at 0.96 V, assigned to the Ru+2/+3 pair. 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{trans-1,4=bis[(4-pyridyl)ethenyl]benzene}(2,2′-bipyridine) Rutherium(ii) Complexes And Their Supramolecular Assemblies With β-cyclodextrin

Two novel ruthenium polypyridine complexes, [Ru(bpy) 2Cl(BPEB)](PF6) and {[Ru(bpy)2Cl] 2(BPEB)}(PF6)2 (BPEB = trans-1,4-bis[2-(4-pyridyl)ethenyl]benzene), were synthesized and their characterization carried out by means of elemental analysis, UV-visible spectroscopy, positive ion electrospray (ESI-MS), and tandem mass (ESI-MS/MS) spectrometry, as well as by NMR spectroscopy and cyclic voltammetry. Cyclic and differential pulse voltammetry for the mononuclear complex showed three set of waves around 1.2 V (Ru2+/3+), -1.0 V (BPEB0/-), and -1.15 (BPEB-/2-). This complex exhibited aggregation phenomena in aqueous solution, involving π-π stacking of the planar, hydrophobic BPEB ligands. According to NMR measurements and variable-temperature experiments, the addition of β-cyclodextrin (βCD) to [Ru(bpy)2Cl(BPEB)] + leads to an inclusion complex, breaking down the aggregatec array.431135213527Juris, A., Balzani, V., Barigelletti, F., Campagna, S., Belser, P., Von Zelewsky, A., (1988) Coord. Chem. Rev., 84, p. 85Balzani, V., Scandola, F., (1991) Supramolecular Photochemistry, , Ellis Horwood: Chichester, U.KWard, M.D., (1995) Chem. Soc. Rev., p. 121Yam, V.W., Lau, V.C., Wu, L., (1998) J. Chem. Soc., Dalton Trans., p. 1461Sun, S.S., Lees, A.J., (2001) Organometallics, 21, p. 31Wilson, L.D., Verral, R.E., (1998) Can. J. Chem., 76, p. 25Dikavar, S., Maheswaran, M.M., (1997) J. Inclusion Phenom., 27, p. 113Salvatierra, D., Jaime, C., Virjili, A., Sánchez-Ferrando, F., (1996) J. Org. Chem., 61, p. 9578Mirzoian, A., Kaifer, A.E., (1997) Chem. Eur. J., 3, p. 1052Loukas, Y.L., (1997) J. Pharm. Pharmacol., 49, p. 944Oh, I., Lee, M., Lee, Y., Shin, S., Park, I., (1998) Int. J. Pharm., 175, p. 215Djedaini, F., Lin, S.Z., Perly, B., Wouessidjewe, D., (1990) J. Pharm. Sci., 79, p. 643Baer, A.J., Macartney, D.H., (2000) Inorg. Chem., 39, p. 1410Wylie, R.S., Macartney, D.H., (1993) Inorg. Chem., 32, p. 1830Harada, A., (2001) Acc. Chem. Res., 34, p. 456Nepogodiev, S.A., Stoddart, J.F., (1998) Chem. Rev., 98, p. 1959Haider, J.M., Chavarot, M., Weidner, S., Sadler, I., Williams, R.M., De Cola, L., Pikramenou, Z., (2001) Inorg. Chem., 40, p. 3912Nelissen, H.F.M., Kercher, M., De Cola, L., Feiters, M.C., Nolte, R.J.M., (2002) Chem. Eur. J., 8, p. 5407Shukla, A., Bajaj, H.C., Das, A., (2001) Angew. Chem., Int. Ed., 40, p. 446Johnson, M.D., Reinsborough, V.C., Ward, S., (1992) Inorg. Chem., 31, p. 1085Ando, I., Ujimoto, K., Kurihara, H., (2001) Bull. Chem. Soc. Jpn., 74, p. 717Scheider, H.-J., Hacket, F., Rüdiger, V., Ikeda, H., (1998) Chem. Rev., 98, p. 1755Bergaman, S.D., Reshef, D., Groysman, S., Goldberg, I., Kol, M., (2002) Chem. Commun., p. 2374Bolger, J., Gourdon, A., Ishow, E., Launay, J.-P., (1996) Inorg. Chem., 35, p. 2937Ishow, E., Gourdon, A., Launay, J.-P., Chiorboli, C., Scandola, F., (1999) Inorg. Chem., 38, p. 1504Sullivan, B.P., Salmon, D.J., Meyer, T.J., (1973) Inorg. Chem., 12, p. 2371Heck, R.F., (1981) Org. React., 27, p. 345Amoroso, A.J., Thompson, A.M.W.C., Maher, J.P., McCleverty, J.A., Ward, M.D., (1995) Inorg. Chem., 34, p. 4828Job, P., (1928) Ann. Chim., 9, pp. 113-134Fielding, L., (2000) Tetrahedron, 56, pp. 6151-6170Scatchard, G., (1949) Ann. N.Y. Acad. Sci., 51, p. 660Cole, R.B., (1997) Electrospray Ionization Mass Spectrometry, , Wiley: New YorkColton, R., D'Agostinho, A., Traeger, J.C., (1995) Mass Spectrom. Rev., 14, p. 79Nikolaou, S., Uemi, M., Toma, H.E., (2001) Spectrosc. Lett., 34, p. 267Maruyama, M., Matsuzawa, H., Kaizu, Y., (1995) Inorg. Chim. Acta, 237, p. 159Constable, E.C., Seddon, K.R., (1983) Inorg. Chim. Acta, 70, p. 251Leising, R.A., Kubow, S.A., Churchill, M.R., Buttrey, L.A., Ziller, J.W., Takeuchi, K.J., (1990) Inorg. Chem., 29, p. 1306Heijden, M., Van Vliet, P.M., Haasnoot, J.G., Reedijk, J., (1993) J. Chem. Soc., Dalton Trans., p. 3675Bates, W.D., Chen, P., Bignozzi, C.A., Schoonover, J.R., Meyer, T.J., (1995) Inorg. Chem., 34, p. 6215Powers, M.J., Meyer, T.J., (1980) J. Am. Chem. Soc., 13, p. 1289Gourdon, A., Launay, J.-P., (1998) Inorg. Chem., 37, p. 5336Franco, M., Araki, K., Rocha, R.C., Toma, H.E., (2000) J. Solution Chem., 29, p. 66

Synthesis, Properties And Gas Phase Collision-induced Dissociation Of The Heptanuclear Doubly Bridged Complex [ru(bpy)2(bpe) 2{ru3o(ch3coo)6(py) 2}2](pf6)4

The [Ru(bpy)2(BPE)2{Ru3O(CH 3COO)6(py)2}2](PF6) 4 complex, in which bpy = 2,2′-bipyridine, BPE = trans-1,2-bis(4-pyridyl)ethylene and py = pyridine, provides an interesting case of a heptanuclear mixed compound containing two triangular [Ru3O] clusters attached to a ruthenium polypyridine center. The composition and structural properties of this doubly bridged complex were investigated by means of electrospray mass (ESI-MS) and tandem mass (ESI-MS/MS) spectrometric experiments and NMR spectroscopy (1H and 13C). The characteristic multi-isotopic distribution, 1/4 m/z peak separation and dissociation chemistry of the isotopologue [Ru(bpy)2(BPE) 2{Ru3O(CH3COO)6(py) 2}2]4+ cation provided detailed and unequivocal MS characterization of the complex. In the electronic spectra of the heptanuclear complex broad bands were observed at 427 and 696 nm, and ascribed, respectively, to [Ru(bpy)2(BPE)2] metal-to-ligand charge-transfer and to [Ru3O] internal cluster transitions. 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A Nitric Oxide Releaser Based On The μ-oxo-hexaacetate-bis(4- Methylpyridine)triruthenium Nitrosyl Complex

The properties of the trinuclear cluster [Ru3OAc 6(pic)2(NO)]PF6 (pic = 4-methyl pyridine, Ac = acetate ion) and the photochemical behavior of the corresponding molecular films are reported in this paper. In this compound, the unpaired π* electron from NO and the unpaired electron from the π-orbitals of the Ru3O unity are strongly coupled; as a consequence, the changes in electronic distribution associated with the several successive redox states promote dramatic effects in the spectroscopic and electrochemical properties of the nitric oxide ligand and the entire complex. NO release has been observed by light irradiation (φ = 0.038 at 365 nm and φ = 0.019 at 468 nm, in acetonitrile solution), changing the original violet color into deep blue. The same behavior has been observed in solid state and in PVA films incorporating this compound, revealing its potential usefulness as NO photoreleaser, as well as for the monitoration of light exposure intensities. © 2004 Elsevier B.V. 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