Rhenium complexes, electron transfer

Macrocyclic receptors made up of two, four or six zinc porphyrins covalently connected have been used as hosts for di- and tetrapyridyl porphyrins, and the association constants are in the range 105-106 M-1, reflecting the cooperative multipoint interactions (84-86). These host-guest complexes have well-defined structures, like Lindsey s wheel and spoke architecture (70, Fig. 27a), and have been used to study energy and electron transfer between the chromophores. A similar host-guest complex (71, Fig. 27b) was reported by Slone and Hupp (87), but in this case the host was itself a supramolecular structure. Four 5,15-dipyridyl zinc porphyrins coordinated to four rhenium complexes form the walls of a macrocyclic molecular square. This host binds meso-tetrapyridyl and 5,15-dipyridyl porphyrins with association constants of 4 x 107 M-1 and 3 x 106 M-1 respectively. 

Infrared spectroelectrochemical technique proved to be an excellent method to look at time and potential dependent changes of various types of chemical species. The employment of this technique will surely be significant on the mechanistic study of electron-transfer reactions of rhenium complexes. 

A few other interesting molecular architectures exhibiting uncharacteristic electrochemical behavior have been constructed on the basis of the methanofullerene building block. These include two methanofullerene-substituted bipyridine ligands complexed to rhenium and ruthenium ((35) and (36) in Fig. 17), which were prepared as possible candidates for photoinduced electron transfer processes [138]. In addition, three fullerene crown ether conjugates ((38), (39), and (40) in Fig. 18) have... 

Tris(l,2-bis(dimethylphosphino)ethane)rhenium(I), [Re(DMPE)3]+ is a simple, symmetrical cation which contains three identical bidentate phosphine ligands. This complex provides a Re(II/I) redox couple with properties that are very convenient for the study of outer-sphere electron transfer reactions.1 Specifically, this couple is stable in both alkaline and acidic media and it exhibits a reversible, one-equivalent redox potential in an accessible region [ °,(II/I) = 565 mV vs. NHE]. Moreover, this complex has been used to obtain information about the biological mechanism of action of 186Re and l88Re radiopharmaceuticals.2,3... 

The reaction of the ketyl radical anion with the oxidized rhenium complex is the energy-releasing electron transfer step. This reaction cannot be carried out separately. While ketyl radical anions are stable species, the oxidized complex is not stable and must be generated as short-lived intermediat. ... 

The luminescence spectra of all receptors in CH3CN were found to be dramatically affected by the addition of acetate or chloride. While compound 19 exhibits an emission decrease, the other receptors 17,18 and 20 show a remarkable intensity increase (up to 500%) with a slight concomitant blue shift of the emission maximum (660 nm for 17). The anion-induced enhancement of luminescence intensity in the case of 17 is clearly due to the decrease of the electron transfer between the ruthenium(II) bipyridyl centre and the quinone moieties. Alternatively, receptors bearing ruthenium or rhenium complexes on the upper rim were also described [20]. 

In view of the strong photo oxidising properties of [Re(phen)(CO)3 (imidazole)]+ (14) (Re(I)VRe(O) = ca. + 1.3 V vs NHE in CH3CN), [Re(phen)(CO)3 (H20)]+ has been reacted with azurin to give [Re(phen)(CO)3(His83)]+-AzCu+, which has been used to study photoinduced electron-transfer reactions [47]. In the absence of quenchers, excitation of the rhenium(I) complex... 

Luminescent ruthenium(II) polypyridine indole complexes such as [Ru (bpy)2(bpy-indole)]2+ (37) and their indole-free counterparts have been synthesised and characterised [77]. The ruthenium(II) indole complexes display typical MLCT (djt(Ru) tt (N N)) absorption bands, and intense and long-lived orange-red 3MLCT (djt(Ru) -> Ti (bpy-indolc)) luminescence upon visible-light irradiation in fluid solutions at 298 K and in alcohol glass at 77 K. In contrast to the rhenium(I) indole complexes, the indole moiety does not quench the emission of the ruthenium(II) polypyridine complexes because the excited complexes are not sufficiently oxidising to initiate electron-transfer reactions. Emission titrations show that the luminescence intensities of the ruthenium(II) indole complexes are only increased by ca. 1.38- to... 

Tables 1 and 2 gives the numerical data for a series of vanadium (II), chromium (III), manganese (IV), molybdenum (III), rhenium (IV), iridium (VI), cobalt (II), and nickel (II) complexes. The first spin-allowed absorption band, caused by an internal transition in the partly filled shell, has the wavenumber equal to A. If spin-forbidden transitions are superposed on this band, a certain distortion from the usual shape of Gaussian error curve can be observed, and one takes the centre of gravity of intensity as the corrected wavenumber ai. One has to be careful not to confuse electron transfer or other strong bands with the internal transitions discussed here. Obviously, one has also to watch for absorption due to other coloured species, produced e. g. by oxidation or hydrolysis of the solutions. In the case of certain octahedral nickel (II), and nearly all tetrahedral cobalt (II) complexes, the first band has not actually been...

V vs. SCE), reductive quenching of the excited complexes by the appended indole ( ,0[indole+,°] < +1.06 V vs. SCE) is favoured by > 0.2-0.4 eV. From this, together with results from transient absorption spectroscopic measurements, it is concluded that the emission quenching of the indole-containing complexes is a result of electron-transfer. The interactions of these rhenium(I) indole complexes with... 

Because the potential of the one-electron reduction of CO2 is — 1.9V (vs. NHE), neither the MLCT excited state nor the OER species of rhenium complexes can reduce CO2 with a single electron through outer-sphere electron transfer. As shown in Eq. (19), however, the potential for obtaining CO by two-electron reduction of CO2 shifts positively to —0.53 V (vs. NHE these potentials of CO2 reduction are close to the values in CH3CN vs. SCE (80)). Such two-electron reduction of CO2 has been reported to proceed efficiently using rhenium(I) complexes as electrochemical catalyst (Eqs. 20-22) (79,85). 

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