2,2 ,2’’-Terpyridyl metal complexes

A typical method for fabricating multiple complex layers is illustrated in Figure 2.11,12 First, an Au/mica or Au/ITO plate is immersed in a chloroform solution of tpy-AB-SS-AB-tpy (tpy=2,2 6, 2" -terpyridyl), providing Au-S-AB-tpy SAM on the plate. In the case of connecting the Fe(II) ion, the tpy-terminated plate is immersed in 0.1 M Fe(BF4)2 aq or (NH4)2Fe(S04)2 aq to form a metal complex. Subsequently, the metal-terminated surface is immersed in a chloroform solution of the ligand Lj or L2 to form a bis(tpy)iron structure (Fig. 2b). The latter two processes are repeated for the preparation of multilayered bis(tpy)iron (II) complex films with linear structures. When L3 is used instead of Lj or L2, the resulting molecular wires have a dendritic structure (Fig. 2c). 

Upon excitation of the metal complex centre, triplet energy transfer to the donor appended porphyrin rapidly quenches the excited state of the central ruthenium bis-terpyridyl unit, whereas excitation of the gold porphyrin, leads in less than 1 ps to the triplet-excited state [23], which is unreactive to-... 

Type II polymers with pendant metal complexes Polymers containing bipyridyl and terpyridyl metal-binding sites... 

Polypyridyl transition metal complexes, especially those of ruthenium(II), have been extensively apphed in light harvesting and information storage, because they exhibit a wide range of photophysical and electrochemical properties. Storrier et al. have reported the synthesis and characterization of PAMAM dendrimers functionalized with tris(bipyridyl) ruthenium(II) (dend- -[Ru(bpy)3] +) or bis (terpyridyl) ruthe-nium(II) (dend-n-[Ru(tpy)2] ) complexes (GO, 1, 2, 3, and 4 with 4, 8, 16, 32,... 

Evidence has been obtained for an inner-sphere mechanism in the iso-electronic peroxodiphosphate (P208 ) ion oxidation of metal complexes. For a series of reactants of the type Fe(LL)a + and Fe(LLL)a + (where LL = bipyridyl or phenanthroline and LLL = terpyridyl), there is no parallel to the outer sphere path observed in the SaOs " oxidation of the same complexes. The mechanism is considered to involve the rate-determining partial dissociation of one of the ligands, with PaOg " (or P04 ) approaching the vacant position, followed by a subsequent fast oxidation reaction. An exception may be in the case of the complex [Ru"(phen)2pyCl]+. In the case of osmium(ii) complexes, however, no reaction takes place in the absence of catalysts since no prior dissociation occurs. 

The Chemistry of Complexes Containing 2.2 -Bipyridy 1, 1,10-Phenanthroline, or 2.2. 6. 2"-Terpyridyl as Ligands W. R. McWhinnie and J. D. Miller Olefin Complexes of the Transition Metals... 

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