Polypyridyls complexes with metals

Anionic guests also perturb the emission properties of transition-metal-based lumophores in host-guest type complexes. Modification of classic ruthenium polypyridyl complexes with anion recognition groups has led to many first-rate examples of anion-sensing complexes for a large... 

The phenylpyridines and polypyridyls are included in Table The dipole moments (p. 127), spectra (p. 136) and ionization constants (p. 147) of these compounds and their 1-oxides, and the ability of the polypyridyls to form complexes with metals (p. 159) have been noted. 

Moucheron C, Kirsch-De Mesmaeker A, Kelly JM (1998) Photophysics and Photochemistry of Metal Polypyridyl and Related Complexes with Nucleic Acids. 92 163-216... 

Numerous metal complexes have been proven to be active electrocatalysts for C02 reduction.1,66-68 These catalysts can be conveniently grouped into three main families metal complexes with polypyridyl ligands, metal complexes with macrocyclic ligands, and metal complexes with phosphorus ligands. 

Alkyl, allyl, and aryl bromides are dehalogenated mainly with the formation of R R dimers in the presence of polypyridyl complexes of the metals of Group VIII. It has been demonstrated that the complexes [Co(bpy)3] + 203-204 [Ni(bpy)3]2+,205 and [Ni(phen)3]2+206 catalyze the reductive dimerization of allyl and alkyl bromides in organic 203 205 206 and aqueous micellar 204 solution. 

The ability of polypyridyl ligands to accept electron density from electron-rich rhenium centers and, thus, to contribute to the stabilization of rhenium complexes with the metal in low oxidation states has already been discussed for rhenium(II) compounds. Only small modifications to the polypyridyl ligand or the metal center can create dramatic differences in the properties of the resulting complexes. Generally, the starting materials which have been introduced as precursors for rhenium(II) polypyridyl complexes in Section 5.3.2.6.2, are also appropriate for the synthesis of related rhenium(l) compounds. 

In the transition metal polypyridyl complex group, tris(4,7-diphenylphen-antroline) ruthenium(II) (Ru(dpp)2+) is widely used as a probe for a PSP. The luminescence lifetime of Ru(dpp)2+ is long compared with the other ruthe-nium(II) polypyridyl complexes [17]. The absorption and emission maxima of Ru(dpp)2+ are 457 and 610 nm, respectively. The luminescence lifetimes under nitrogen- and air-saturated conditions are ca. 4.0 and 2.0 ps, respec-... 

Because of the presence of a well-defined energy gap between the conduction and the valence band, semiconductors are ideally suited for investigation of the interfacial interactions between immobilized molecular components and solid substrates. In this chapter, interfacial assemblies based on nanocrystalline TiOz modified with metal polypyridyl complexes will be specifically considered. It will be shown that efficient interaction can be obtained between a molecular component and the semiconductor substrate by a matching of their electronic and electrochemical properties. The nature of the interfacial interaction between the two components will be discussed in detail. The application of such assemblies as solar cells will also be considered. The photophysical processes observed for interfacial triads, consisting of nanocrystalline TiO 2 surfaces modified with molecular dyads, will be discussed. Of particular interest in this discussion is how the interaction between the semiconductor surface and the immobilized molecular components modifies the photophysical pathways normally observed for these compounds in solution. 

Balzani et al. (70) employed a strategy focusing on complexes as metals and as ligands (71,72), for developing a number of interesting supramolecular systems. Ditopic polypyridyl ligands, for example, 2,3- and 2,5-dipyridylpyrazine (2,3-dpp and 2,5-dpp), 2,2 -biquinoline (biq), tetrapyrido[3,2-fl 2, 3 -c 3",2"-/z 2", 3 "-/]-phenazine (73,74) (tppz), and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (75-77) (tpypz), in combination with monotopic ligands (e.g., bpy and phen) were utilized in the preparation of a number of homo- and heteropolynuclear complexes of well-defined structures (Fig. 2). 

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