Ruthenium optical properties

Most photosensitizers, however, are reasonably photostable compounds, and their optical properties have been studied in depth. In particular, there has been much interest in ruthenium-based photosensitizers such as [Ru(bpy)3]2+ and [Ru(phen)3]2+, due to their stability and absorption of visible light. Detailed information on their optical properties, including ground and excited state information in relation to photosensitization, has been reviewed by Creutz et al. [16]. Similarly, the photochemistry and photophysics of rhenium complexes, as discussed here, have been reviewed in detail by Kirgan et al. [7]. 

Coe, B. J., Jones, L. A., Harris, J. A., et al., Syntheses and spectroscopic and quadratic nonlinear optical properties of extended dipolar complexes with ruthenium(II) ammine electron donor and N-methylpyridinium acceptor groups. J. Am. 

The physical and optical properties of the NPs used in this investigation are described in Table 6.1. The optical absorption properties of the ruthenium dye complex are also detailed in the table. It can be seen that there is good overlap between 7 of the pure silver and alloy NPs and the absorption band of the complex, while the gold NPs lie outside the absorption peak and are used as a negative control. The dependence of the excitation spectra of the dye complex on NP-dye distance is shown in Figure 6.14 for the case of the pure silver NPs. Also included in the figure is the excitation spectrum for the complex coated on the PEL layer in the absence of NPs. From Table 6.1, it can be seen that there is very good overlap between 7 of the silver NPs and the dye absorption band which constitutes the optimum plasmonic enhancement condition for the case of excitation enhancement. 

Coe, B.J., Harris, J.A., Asselberghs, I., Persoons, A., Jeffery, J.C., Rees, L.H., Gelbrich, T., Hursthouse, M.B. Tuning of charge-transfer absorption and molecular quadratic nonhnear optical properties in ruthenium(II) ammine complexes. J. Chem. Soc., Dalton Trans. 3617-3625 (1999)... 

Sakaguchi, H., Nagamura, T., Matsuo, T. Quadratic nonhnear optical properties of ruthenium(ll)-bipyridine complexes in crystalhne powders. Appl. Organomet. Chem. 5, 257—260 (1991)... 

Le Bouder, T., Maury, O., Bondon, O., Costuas, K., Amouyal, E., Ledoux, I., Zyss, J., Le Bozec, H. Synthesis, photophysical and nonlinear optical properties of macromolecular architectures featuring octupolar tris(bipyridine) ruthenium(II) moieties evidence for a supramolecular sell-ordering in a dentritic structure. J. Am. Chem. Soc. 125, 12284-12299 (2003)... 

Jiang, C.-W., Chao, H., Li, R.-H., Li, H., Ji, L.-N. Syntheses, characterization and third-order nonlinear optical properties of ruthenium(II) complexes containing 2-phenylimidazo-[4,5-/][l,10]phenanthroline and extended diimine ligands. Polyhedron 20, 2187-2193 (2001)... 

Powell, C.E., Cifuentes, M.P., Morrall, J.P., Stranger, R., Humphrey, M.G., Samoc, M., Luther-Davies, B., Heath, G.A. OrganometalUc complexes for nonlinear optics. 30. Electrochromic Unear and nonlinear optical properties of alkynylbis(diphosphine)ruthenium complexes. J. Am. Chem. Soc. 125, 602-610 (2003)... 

Grund, A., Kaltbeitzel, A., Mathy. A.. Schwarz, R., Bubeck, C., Vermehren, P., Hanack, M. Resonant nonlinear optical properties of spin-cast films of soluble oligomeric bridged (phthalo-cyaninato)ruthenium(II) complexes. J. Phys. Chem. 96, 7450-7454 (1992)... 

Coe, B.J., Harries, J.L., Harris, J.A., Brunschwig, B.S., Coles, S.J., Light, M.E., Hrrrsthouse, M.B. Syntheses, spectroscopic and molecular quadratic nonlinear optical properties of dipolar ruthenium(II) complexes of the ligand l,2-phenylenebis(dimethylarsine). Dalton Trans. 2935-2942 (2004)... 

Platinum polyynes represent one of the most interesting and well-studied classes of linear metallopolymers (Chapters, Section 5.2). Dendritic analogues of these materials have been prepared by a variety of methodologies [94—96]. One example is the nonametallic dendrimer 8.43, which was prepared by a convergent route as illustrated in Eq. 8.9 [94]. Dendrimers based on ruthenium polyyne architectures have also been prepared, and promising nonlinear optical properties have been identified [97, 98]. 

Optical Properties. The optical reflectivity of Ru is near that of Rh (Fig. 3.1-333). Ruthenium alloyed to Pd enhances the optical reflectivity by 4-5% (Fig. 3.1-275). 

More recently, a soluble polymer (32) was prepared via reaction of l,l -ferrocenedimethanol with 4,4 -biphenyltetraamine in the presence of [RuCl2(P(C6115)3)3] (70). Approximately 20% of the iron centers were foimd to be in the Fe(III) state as a result of oxidation by ruthenium complexes formed during the polycondensation reaction. Wright and co-workers have reported the synthesis of ferrocene-based polymers possessing nonlinear optical properties (33) (71-73). These polymers were formed by polycondensation of a difunctionabzed ferrocene monomer (71). 

The DSSC is one of the most-studied types of emerging SCs. Initially, ruthenium dyes were used. Then, porphyrin dyes found widespread application in DSSCs because of their favorable optical properties and chemical bond flexibility. Efficiency of these DSSCs was not much impressive until mid-2000. Progress in a molecular design and synthesis of new porphyrins as well as preparation of new more efficient charge mediators allowed improving this efficiency dramatically. This improvement was mostly due to introduction of the push-pull structured and 71-extended peripheral substituents. The recent research focuses on enriching absorbance spectra of MPs. It resulted in efficiency of DSSCs with MPs equal to those with the ruthenium dyes. 

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