- A high molar extinction coefficient mono-anthracenyl bipyridyl heteroleptic ruthenium(II) complex: Synthesis, photophysical and electrochemical properties
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In our quest to develop good materials as photosensitizers for photovoltaic dye-sensitized solar cells (DSSCs), cis-dithiocyanato-4-(2,3-dimethylacrylic acid)-2,2'- bipyridyl-4-(9-anthracenyl-(2,3-dimethylacrylic)-2,2'-bipyridyl ruthenium(II) complex, a high molar extinction coefficient charge transfer sensitizer, was designed, synthesized and characterized by spectroscopy and electrochemical techniques. Earlier studies on heteroleptic ruthenium(II) complex analogues containing functionalized oligo-anthracenyl phenanthroline ligands have been reported and documented. Based on a general linear correlation between increase in the length of p-conjugation bond and the molar extinction coefficients, herein, we report the photophysical and electrochemical properties of a Ru(II) bipyridyl complex analogue with a single functionalized anthracenyl unit. Interestingly, the complex shows better broad and intense metal-to ligand charge transfer (MLCT) band absorption with higher molar extinction coefficient (δmax = 518 nm, σ = 44900 M-1cm-1), and appreciable photoluminescence spanning the visible region than those containing higher anthracenyl units. It was shown that molar absorption coefficient of the complexes may not be solely depended on the extended p-conjugation but are reduced by molecular aggregation in the molecules.
- Adeloye, Adewale O.,Ajibade, Peter A.
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- Synthesis and characterization of a new ditopic bipyridine-terpyridine bridging ligand using a Suzuki cross-coupling reaction
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Synthesis of a new bridging ligand 4'-{4-[(2,2'-bipyridin)-4-yl]-phenyl}-2,2':6'-2''-terpyridine (I) was reported. A Suzuki cross-coupling reaction was conducted for the preparation of such ligand in two different routes either between 4'-(4-bromophenyl)-2,2':6'-2''-terpyridine and 2,2'-bipyridyl-4-boronic acid or 4'-(4-boronatophenyl)-2,2':6',2''-terpyridine and 4-bromo-2,2'-bipyridine. Br HO OH B + N N N N N N N HO OH B Br N + N N N (I) N N N N
- Zibaseresht, Ramin
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- Synthesis and spectral properties of ruthenium(II) complexes based on 2,2′-bipyridines modified by a perylene chromophore
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Five new 2,2′-bipyridines functionalized with a perylene or a perylenediimide moiety were synthesized and the corresponding heteroleptic ruthenium(II) complexes ([Ru(bpy)2(L)](PF6)2; bpy = 2,2′-bipyridyl, L = perylene-substituted bpy ligand) were prepared. The UV-vis spectra of the ruthenium(II) complexes showed red-shifted and intense absorption bands derived from the conjugated structure of the new ligands.
- Kodama, Koichi,Kobayashi, Akinori,Hirose, Takuji
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- Synthesis and optical properties of bifunctional thiophene molecules coordinated to ruthenium
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(Chemical Equation Presented) A series of unsymmetrical bi- and tetrathiophenes have been synthesized with bipyridine and phosphonic acid functional groups. To do this, phosphonic esters were bonded to thiophenes and the thiophenes coupled to bipyridine. After synthesis of the thienylbipyridines, bis(bipyridine) ruthenium was coordinated to them through the bipyridines. The thienylbipyridines absorb visible light and fluoresce; however, on attachment to ruthenium, both their fluorescence and that of ruthenium are quenched. An additional effect of coordinating ruthenium to the thiophenes is a new absorption band around 470 nm. Variation in oligothiophene length and bipyridine substitution position allowed comparison of the effect of these variables on electronic properties. The longer oligothiophenes display lower-energy absorptions and emissions than that of the shorter thiophenes. In contrast, the position of the bipyridine attachment does not have a large effect on the absorbance or emission wavelength, or on the fluorescence quantum yield.
- Bair, Joseph S.,Harrison, Roger G.
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- Stereoselective and hierarchical self-assembly from nanotubular homochiral helical coordination polymers to supramolecular gels
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A new binaphthylbisbipyridine-based ligand underwent diastereoselective self-assembly with silver(i) ions to form nanotubular homochiral helical coordination polymers, which further hierarchically self-assemble into nanofibers, capable of immobilizing organic solvents.
- He, Yabing,Bian, Zheng,Kang, Chuanqing,Gao, Lianxun
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- Microwave assisted synthesis of 3-(2,2′-bipyridine-4-yl)-2-propenoic acid ethyl ester
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Abstract: 3-(2,2′-Bipyridine-4-yl)-2-propenoic acid ethyl ester which may be used for the introduction of metal coordination sites in polyacrylates is synthesized by an improved synthetic route to the key intermediate 4-bromo-2,2′-bipyridine working under microwave conditions, which leads to drastic shortening of reaction times, as well as to the reduction of reaction steps. In addition, a synthetic procedure to formyl-bipyridines that is not based on reductive or oxidative reaction conditions could be applied. Starting from the formyl-bipyridine derivative the title compound may be effectively generated using modified Horner–Wadsworth–Emmons reaction conditions to yield the new ligand. Graphical abstract: [Figure not available: see fulltext.].
- Heintz, Katharina,Imhof, Wolfgang,G?rls, Helmar
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- Click chemistry on a ruthenium polypyridine complex. An efficient and versatile synthetic route for the synthesis of photoactive modular assemblies
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In this Communication, we present the synthesis and use of [Ru(bpy) 2(bpy-CCH)]2+, a versatile synthon for the construction of more sophisticated dyads by means of click chemistry. The resulting chromophore-acceptor or -donor complexes have been studied by flash photolysis and are shown to undergo efficient electron transfer to/from the chromophore. Additionally, the photophysical and chemical properties of the original chromophore remain intact, making it a very useful component for the preparation of visible-light-active dyads.
- Baron, Aurelie,Herrero, Christian,Quaranta, Annamaria,Charlot, Marie-France,Leibl, Winfried,Vauzeilles, Boris,Aukauloo, Ally
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- A boronic acid-diol interaction is useful for chiroselective transcription of the sugar structure to the Δ- Versus Λ-[CoIII(bpy)3]3+ ratio
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In order to apply boronic acid-saccharide interactions to the chiroselective synthesis of Δ- and Λ-[CoIII(bpy)3]3+ saccharide-binding ligands, 2,2′-bipyridine-4-boronic acid (bpymb) and 2,2′-bipyridine-4,4′-diboronic acid (bpydb) were newly synthesized. It was shown that most D-saccharides form cyclic 1:1 complexes with bpydb to afford the CD-active species. The positive exciton coupling band implies that two pyridine rings are twisted in a clockwise direction ((R)-chirality). In contrast, such a CD-active species was not yielded from bpymb. The treatment of the bpydb-D-saccharide complexes with Co(OAc)2 gave the substitution-active [CoII(bpyba)3]4--saccharide complexes, which were oxidized to the substitution-inactive [CoIII(bpyba)3]3--saccharide complexes. In this stage, the Δ vs. Λ ratio was fixed. The complexes were converted to [CoIII(bpy)]3+ by treatment with AgNO3 and the e.e. was determined by comparison with authentic Δ- or Λ-[CoIII(bpy)]3+. The Δ-isomer was obtained in excess from most D-saccharides but the Λ-isomer was also obtained from D-fructose and D-fucose. At 4°C, the largest e.e. for bpydb was attained with D-glucose (47% e.e.; Δ excess). Under the same reaction conditions the bpymb + D-glucose system gave 16% e.e. (Δ excess). The e.e. of the bpydb + D-glucose system increased with lowering the reaction temperature and at -25°C it reached 79% e.e. The foregoing results clearly establish that the saccharide-templated synthesis is useful as a new concept for the preparation of chiral tris(2,2′-bipyridine)-metal complexes. Furthermore, the Δ vs. Λ equilibrium can be shifted in either direction by the selection of saccharide enantiomers.
- Mizuno, Toshihisa,Takeuchi, Masayuki,Hamachi, Itaru,Nakashima, Kazuaki,Shinkai, Seiji
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- Conducting redox polymers: Investigations of polythiophene-Ru(bpy)3(n+) hybrid materials
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A series of thiophene-appended Ru(II)(bpy)3 derivatives, Ru(1)3, Ru(2)3, Ru(3)3, Ru(bpy)2(1), and Ru(bpy)2(2), and their resulting polymers have been synthesized and characterized. The bpy ligands 5,5'-bis (5-(2,2'-bithienyl))-2,2'-bipyridine, 1, 4,4'-bis (5-(2,2'-bithienyl))-2,2'- bipyridine, 2, and 4-(5-(2,2'-bithienyl))-2,2'-bipyridine, 3, all contain electrochemically polymerizable bithienyl moieties. The monomers Ru (2)3, Ru(3)3, Ru (bpy)2(1) and Ru(bpy)2(2) display spectroscopic features that are similar to the ligand-based and MLCT bands found for Ru(bpy)3. The cyclic voltammograms of all of these polymers display both metal-centered and thiophene-based electroactivity. High redox conductivity was found in poly(Ru(2)3) and poly(Ru(3)3) for both the thiophene-based oxidation and metal-based reduction processes. These results indicate that the polymers display charge localization for both the metal complexes as well as the tetrathienyl connecting units. The degree of interconnection (number of linkages) as well as the substitution pattern were found to control the conductivity of these polymers. The highest conductivity (3.3 x 10-3 S cm- 1) was found for poly(Ru(2)3), which is able to have up to 6 linkages with other ruthenium complexes as well as possessing a 4,4'-substitution pattern that allows effective orbital overlap of the conjugated polymer backbone with the ruthenium centers.
- Zhu, Sherry S.,Kingsborough, Richard P.,Swager, Timothy M.
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- Sensitizer-catalyst assemblies for water oxidation
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Two molecular assemblies with one Ru(II)-polypyridine photosensitizer covalently linked to one Ru(II)(bda)L2 catalyst (1) (bda = 2,2′-bipyridine-6,6′-dicarboxylate) and two photosensitizers covalently linked to one catalyst (2) have been prepared using a simple C-C bond as the linkage. In the presence of sodium persulfate as a sacrificial electron acceptor, both of them show high activity for catalytic water oxidation driven by visible light, with a turnover number up to 200 for 2. The linked photocatalysts show a lower initial yield for light driven oxygen evolution but a much better photostability compared to the three component system with separate sensitizer, catalyst and acceptor, leading to a much greater turnover number. Photocatalytic experiments and time-resolved spectroscopy were carried out to probe the mechanism of this catalysis. The linked catalyst in its Ru(II) state rapidly quenches the sensitizer, predominantly by energy transfer. However, a higher stability under photocatalytic condition is shown for the linked sensitizer compared to the three component system, which is attributed to kinetic stabilization by rapid photosensitizer regeneration. Strategies for employment of the sensitizer-catalyst molecules in more efficient photocatalytic systems are discussed.
- Wang, Lei,Mirmohades, Mohammad,Brown, Allison,Duan, Lele,Li, Fusheng,Daniel, Quentin,Lomoth, Reiner,Sun, Licheng,Hammarstr?m, Leif
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- Synthesis, photophysical and electrochemical properties of a mixed bipyridyl-phenanthrolyl ligand Ru(II) heteroleptic complex having trans-2-Methyl-2-butenoic acid functionalities
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In this work, two ligands: 4-(trans-2-Methyl-2-butenoic acid)-2,2'-bipyridine) (L1) and 5-(trans-2-methyl-2-butenoic acid)-1,10-phenanthroline (L2), with the corresponding mixed-ligand heteroleptic Ru(II) complex were synthesized and characterized by FT-IR, 1H-, 13C-NMR spectroscopy and elemental analysis. The influence of the mixed functionalized polypyridyl ruthenium(II) complex on the photophysical and electrochemical properties were investigated and compared to individual single-ligand homoleptic complexes. Interestingly, the mixed-ligand complex formulated as [RuL1L2(NCS)2] exhibits broad and intense metal-to-ligand charge transfer (MLCT) absorption with a high molar extinction coefficient (λmax = 514 nm, ε = 69,700 M -1 cm-1), better than those of individual single-ligand complexes, [Ru(L1)2(NCS)2] and [Ru(L2) 2(NCS)2], and a strong photoluminescence intensity ratio in the red region at λem = 686 nm. The electrochemical properties of the complex indicated that the redox processes are ligand-based.
- Adeloye, Adewale O.
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- Recyclable Transition Metal Catalysis using Bipyridine-Functionalized SBA-15 by Co-condensation of Methallylsilane with TEOS
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Well-defined recyclable Pd- and Rh-bipyridyl group-impregnated SBA-15 catalysts were prepared for C?C bond coupling reaction and selective hydrogenation reactions, respectively. These SBA-15 derived ligands for the catalysts were prepared by direct and indirect co-condensation method using bipyridyl-linked methallylsilane. This indirect method, involving methoxysilane generated from methallylsilane shows higher loading efficiency of transition metal catalysts on SBA-15 than the direct use of methallylsilane.
- Han, Ye Ri,Kim, Jae Soon,Park, Woo-Jin,Lee, Chang-Hee,Cheon, Jinwoo,Jun, Chul-Ho
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p. 197 - 201
(2021/01/18)
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- Synthesis of a novel dinuclear ruthenium polypyridine dye for dye-sensitized solar cells application
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A new dinuclear ruthenium(II) polypyridine complex has been successfully synthesized. The new compound has been characterized by spectroscopic and electrochemical methods. Its potential application as a sensitizing dye in dye-sensitized solar cells has been checked under AM 1.5 G irradiation conditions (100 mW cm-2) and its performance was compared to that of a commercially available mononuclear analogous dye. The overall light-to-electricity conversion efficiency of the photovoltaic device sensitized by the new dinuclear dye has been found to be over 2.5 times lower than that sensitized by the commercial analogue, despite a much higher extinction coefficient of the former dye. The probable reasons for the lower photovoltaic activity are discussed.
- Zalas,Gierczyk,Klein,Siuzdak,P?dziński,?uczak
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p. 381 - 387
(2013/11/06)
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- 2-Nitroimidazole-ruthenium polypyridyl complex as a new conjugate for cancer treatment and visualization
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A novel long-lifetime highly luminescent ruthenium polypyridyl complex containing 2-nitroimidazole moiety [Ru(dip)2(bpy-2-nitroIm)]Cl 2 (dip = 4,7-diphenyl-1,10-phenanthroline, bpy-2-nitroIm = 4-[3-(2-nitro-1H-imidazol-1-yl)propyl]-2,2′-bipyridine) has been designed cancer treatment and imaging. The luminescence properties of the synthesized compound strongly depend on the oxygen concentration. Under oxygen-free conditions quantum yield of luminescence and the average lifetime of emission were found to be 0.034 and 1.9 μs, respectively, which is ca. three times higher in comparison to values obtained in air-equilibrated solution. The binding properties of the investigated ruthenium complex to human serum albumin have been studied and the apparent binding constant for the formation of the protein-ruthenium adduct was determined to be 1.1 × 105 M - 1. The quantum yield and the average lifetime of emission are greatly enhanced upon binding of ruthenium compound to the protein. The DNA binding studies revealed two distinguished binding modes which lead to a decrease in luminescence intensity of ruthenium complex up to 60% for [DNA]/[Ru] 80. Preliminary biological studies confirmed fast and efficient accumulation of the ruthenium complex inside cells. Furthermore, the ruthenium complex was found to be relatively cytotoxic with LD50 of 12 and 13 μM for A549 and CT26 cell lines, respectively, under normoxic conditions. The retention and cellular uptake of ruthenium complex is enhanced under hypoxic conditions and its LD 50 decreases to 8 μM for A549 cell line.
- Mazuryk, Olga,Maciuszek, Monika,Stochel, Grazyna,Suzenet, Franck,Brindell, Ma?gorzata
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- Modular syntheses of star-shaped pyridine, bipyridine, and terpyridine derivatives by employing sonogashira reactions
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A simple and flexible synthesis for a series of star-shaped pyridine, bipyridine, and terpyridine derivatives is reported by using a modular approach that combines the use of a ligand, spacer, and core unit. A fairly efficient method to prepare 4′-nonafloxy-functionalized terpyridine derivatives is described. The building blocks that contain the functionalized pyridine, bipyridine, or terpyridine derivatives were linked to different C3-symmetrical core units. In most cases, Sonogashira reactions were employed in the crucial final steps of the synthesis. A star-shaped dodecafluorinated compound was also prepared in a straightforward fashion. A simple procedure for the preparation of partially silylated 1,3,5-triethynylbenzene derivatives is presented, which provides an approach to C2-symmetrical star-shaped compounds that have only one terpyridine and two terphenyl units as "dummy" ligands. The absorption and emission spectra of the fully conjugated C3-symmetrical pyridine derivatives were systematically investigated, and fairly large Stokes shifts were observed.
- Trawny, Daniel,Kunz, Valentin,Reissig, Hans-Ulrich
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supporting information
p. 6295 - 6302
(2015/03/30)
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- ORGANIC METAL DYE, AND PHOTOELECTRIC ELEMENT AND DYE-SENSITIZED SOLAR CELL USING THE ORGANIC METAL DYE
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The present invention relates to an organic metal dye comprising fused heterocyclic derivatives, and to a photoelectric element and to a dye-sensitized solar cell using the organic metal dye.
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- Synthesis of new dendritic antenna-like polypyridine ligands
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An efficient synthesis of multidentate polypyridine ligands, 3,5-bis(2,2′-bipyridin-4-ylethynyl)benzoic acid and 3,5-bis(2,5-bis(2- pyridyl)-pyridin-4-ylethynyl)benzoic acid, with potential application in the production of ruthenium dyes for dye-sensitised solar cells was developed. Isolation of intermediate products and final compounds is simple and the yields are very high. The ligands obtained can be used in the synthesis of dendritic analogues of well known and very efficient N3 dye and "black dye".
- Zalas, Maciej,Gierczyk, Blazej,Ceglowski, Michal,Schroeder, Grzegorz
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p. 733 - 740
(2013/07/26)
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- Polymeric transition metal complexes and uses thereof
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Novel polymeric transition metal complexes of iron, cobalt, ruthenium, osmium, and vanadium are described. The polymeric transition metal complexes can be electron transfer mediators in enzyme-based electrochemical sensors. In such instances, transition metal complexes accept electrons from, or transfer electrons to, enzymes at a high rate and also exchange electrons rapidly with the sensor.
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- From 1,2,4-triazines and tributyl(ethynyl)tin to stannylated bi- and terpyridines: The cycloaddition pathway
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Recently, we reported on cycloadditions between electron-deficient heterodienes and tributyl(ethynyl)tin, which provide a new pathway to stannylated pyridazines and, in one special case, pyridines. In order to broaden the synthetic scope of these reactions, we have developed hetero [4+2] cycloaddition reactions between a number of tailor-made 1,2,4-triazines 5-9 (acting as heterodienes), and tributyl(ethynyl)tin (acting as dienophile). The desired 1,2,4triazines are readily available, in moderate to very good yields, by the condensation reactions of appropiate carbamidrazones and glyoxals. These cycloadditions open up a novel route to regiospecifically stannylated 2,2'-bi- and 2,2',6',2''-terpyridines 1-4, 11 in good yields. The stannanes 1-4, 11 are versatile synthetic intermediates, and with this strategy various substituents can be incorporated directly by substitution of the stannyl group, as was shown for halogens and carbon electrophiles under Stille conditions.
- Sauer, Juergen,Heldmann, Dieter K.,Pabst, Gunther R.
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p. 313 - 321
(2007/10/03)
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- Functionalization of 2,2'-bipyridines in their 4 and 5 positions. Synthesis of 5-Ethynyl-2,2'-Bipyridine
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The synthesis of 5-ethynyl-2,2'-bipyridine (9) from 5methyl-2.2'- bipyridine (5) is reported. The conversion of the methyl derivative, which is the most common starting material to further substitution, involves the preparation of 2,2'-bipyridine-5-carbaldehyde (6). Corey-Fuchs olefination and subsequent hydrolysis yields the target compound 9. The multistep synthesis is discussed with respect to alternative routes and compared with those of related 4-substituted 2,2'-bipyridines.
- Polin, Johann,Schmohel, Erich,Balzani, Vincenzo
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p. 321 - 324
(2007/10/03)
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- LUMINESCENT METAL COMPLEXES. PART 1. TRIS-CHELATES OF SUBSTITUTED 2,2'-BIPYRIDYLS WITH RUTHENIUM(II) AS DYES FOR LUMINESCENT SOLAR COLLECTORS
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Ruthenium(II) and osmium(II) complexes of 2,2'bipyridyls (bipy) and 1,10-phenanthrolines (phen) are identified as feasible dyes for use in luminecsent solar collectors.Twenty-seven RuII)bipy)32+ complexes are prepared and the absorption and emission spectra of their solutions in EtOH-MeOH at room temperature are reported.Quantum efficiencies, wich are sensitive to oxygen quenching, vary between 0.002 and 0.306 depending upon substituents.The effect of the medium on the spectral properties of selected compounds has also been investigated.Measured quantum yields of non-aqueous solutions are higher than those for aqueous solutions but lower than for doped plastic films.
- Cook, Michael J.,Lewis, Anthony P.,McAuliffe, Glenn S. G.,Skarda, Vladimir,Thomson, Andrew J.,et. al.
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p. 1293 - 1302
(2007/10/02)
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