Ruthenium terpyridine complex

Finally, conjugated materials 40 based on poly(phenylene thiophene) and poly (fluorene thiophene) main chain polymers functionalized with pendant trithiocyanato ruthenium terpyridine complexes were synthesized by the Suzuki coupling reaction. Heterojunction photovoltaic cells with the simple structure ITO/polymer/C-60/Al were fabricated. Under simulated AM1.5 solar light illumination, the short circuit currents, open circuit voltages, and power conversion efficiencies of the photovoltaic cells were measured to be 1.53-2.58 mAcm 2, 0.12-0.24 V, and 0.084-0.12%, respectively [77]. 

The oxidation of both aliphatic and aromatic amines to nitriles by O2 or air in the presence of the Ru2Cl4(az-tpy)2 complex indicates that the conversion is strongly influenced by the alkyl chain length. The amines with shorter chain had lower conversions than those with longer chains. Further, the ruthenium terpyridine complex functionalized with azulenyl moiety at the 4-position of the central pyridine core provided a much higher catalytic reactivity compared with a series of ruthenium terpyridine complexes. The use of deuterated benzylamine demonstrated the importance of RuOH in the mechanism of the reaction." ... 

Vectorial transfer of electronic energy in rod-like ruthenium-osmium complexes with bis-2,2, 2"-terpyridine ligands 97CC333. 

In a very recent set of papers [48,54,59,60,131,132,324-328], the synthesis and characterization of metallosupramolecular amphiphilic block copolymers containing a hydrophilic PEO block linked to a hydrophobic PS or PEB block through a fozs-2,2/ 6/,2/terpyridine-ruthenium(II) complex have been described. These copolymers form the so-called metallosupramolecular micelles . 

The fozs-2,2/ 6/,2/terpyridine-ruthenium(II) complexes are assumed to be located at the core/corona interface, as schematically depicted in Fig. 23. 

Clustering in PS-[Ru]-PEO micelles was shown to be sensitive to temperature and ionic strength, as previously observed for covalent PS-PEO copolymer [131]. These effects were, however, more pronounced in the case of the metallosupramolecular copolymers, indicating a possible influence of the charged fois-2,2/ 6/,2/terpyridine-ruthenium(II) complexes [329]. 

Fluorescent redox switches based on compounds with electron acceptors and fluorophores have been also reported. For instance, by making use of the quinone/ hydroquinone redox couple a redox-responsive fluorescence switch can be established with molecule 19 containing a ruthenium tris(bpy) (bpy = 2,2 -bipyridine) complex.29 Within molecule 19, the excited state of the ruthenium center, that is, the triplet metal-to-ligand charge transfer (MLCT) state, is effectively quenched by electron transfer to the quinone group. When the quinone is reduced to the hydroquinone either chemically or electrochemically, luminescence is emitted from the ruthenium center in molecule 19. Similarly, molecule 20, a ruthenium (II) complex withhydroquinone-functionalized 2,2 6, 2"-terpyridine (tpy) and (4 -phenylethynyl-2,2 6, 2"- terpyridine) as ligands, also works as a redox fluorescence switch.30... 

Figure 10.8 shows the example ofa ruthenium(ii) bis-terpyridine complex that acts as the scaffold for a biscarboxylate recognition site 22 [62]. 

However, this is not to say that it is impossible to alkylate cationic complexes. The reaction of the ruthenium(n) complex [Ru(5.16)2]2+, in which only the three chelating nitrogen atoms of the 2,2 6 ,2"-terpyridine moiety are co-ordinated to the metal, with iodomethane in acetonitrile gives the alkylated product [Ru(5.17)2]4+ in near quantitative yield. 

Despite the extensive application of ruthenium complexes in DSSC, transition metal containing polymers have received relatively little attention in the fabrication of polymeric photovoltaic cells. Most of the early works on ruthenium containing polymers were focused on the light-emitting properties.58-60 Several examples of ruthenium terpyridine/bipyridine containing conjugated polymers and their photoconducting/electroluminescent properties were reported.61,62... 

All these polymers with ruthenium terpyridine/bipyridine complexes contain ionic ruthenium complex on the polymer main chain. Other than the... 

Barigelletti F et al (1993) Luminescence properties of rigid rod-like binuclear ruthenium(II)-osmium(II) terpyridine complexes - electronic interaction through phenyl bridges. JCS Chem Commun 942-944... 

Ding H-Y, Wang X-S, Song L-Q, et al. Aryl-modified ruthenium bis(terpyridine) complexes Quantum yield of 02 generation and photocleavage on DNA. J Photochem Photobiol A Chem 2006 177 286-94. 

The systems described above all involve peroxometal species as the active oxidant. In contrast, ruthenium catalysts involve a ruthenium-oxo complex as the active oxidant [1]. Until recently, no Ru-catalysts were known that were able to activate H202 rather then to decompose it. However in 2005 Beller and co-workers recognized the potential of the Ru(terpyridine)(2,6-pyridinedicarboxylate) catalyst [63] for the epoxidation of olefins with H202 [64]. The result is a very efficient method for the epoxidation of a wide range of alkyl substituted or allylic alkenes using as little as 0.5 mol% Ru. In Fig. 4.26 details are given. Terminal... 

Such multistep synthesis, the key step of which involved the reaction of the ruthenium(II) complex of 5,5"-bis(4-hydroxyphenyl)terpyridine (Ru.15 " ) with two equivalents of the diiodo derivative of hexaethylene glycol afforded the target catenate Ru.16. The electrochemical data obtained for Ru.16 and its open-chain precursor Ru.15 are summarized in Table 8, along with those of [Ru(tpy)2] + (tpy = 2,2 6, 2"-terpyridine) given for comparison. 

Sauvage, J. P. Collin, J. P. Chambron, J. C. Guillerez, S. Coudret, C. Balzani, V. Barigelletti, F. Decola, L. Flamigni, L. Ruthenium(II) and osmium(II) bis(terpyridine) complexes in covalently linked multicomponent systems - synthesis, electrochemical behavior, absorption spectra, and photochemical and photophysical properties. Chem. Rev. 1994, 94, 993-1019. 

As with chromophores, the steric encapsulation of a dendrimer core can be utilized to prevent intermolecular interactions between redox active sites. A number of different redox active core moieties have been investigated, including, iron—sulfide clusters,9394 bis(terpyridine)iron(II) complexes,92 tris-(bipyridine)ruthenium(II) complexes,330 zinc porphyrins,252 oligothienylenevinylenes,331 fullerenes,236,332 ferrocenes,333-336 oligothiophenes,322 oligonaphtha-lenes,337 and 4,4 -bipyridinium.338... 

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