Synthesis and characterizations of cyclometalated iridium(III) solvento complexes

Complexes of the type [Ir(L)[sub 2](S)[sub 2]][OTf] have been prepared by reactions of [Ir(L)[sub 2]Cl][sub 2] with AgOTf in an appropriate solvent medium (L = 2-phenylpyridine (ppy) or 2-(p-tolyl)pyridine (ptpy); S = H[sub 2]O or CH[sub 3]CN; OTf = CF[sub 3]SO[sub 3][sup [minus]]). These solvento c...

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Veröffentlicht in:Inorganic chemistry 1994-01, Vol.33 (1), p.9-14
Hauptverfasser: Schmid, B, Garces, F. O, Watts, R. J
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Sprache:eng
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Zusammenfassung:Complexes of the type [Ir(L)[sub 2](S)[sub 2]][OTf] have been prepared by reactions of [Ir(L)[sub 2]Cl][sub 2] with AgOTf in an appropriate solvent medium (L = 2-phenylpyridine (ppy) or 2-(p-tolyl)pyridine (ptpy); S = H[sub 2]O or CH[sub 3]CN; OTf = CF[sub 3]SO[sub 3][sup [minus]]). These solvento complexes have been characterized by [sup 1]H and [sup 13]C NMR spectroscopies, UV-visible absorption and emission spectroscopies, and cyclic voltammetry. Estimates of radiative lifetimes based upon weak integrated absorption bands in the 460-490 nm region are in agreement with emission lifetimes monitored in glasses at 77 K. Low-lying excited states responsible for these absorption and emission bands are assigned to an admixture of ligand-localized and metal-to-ligand charge-transfer character. Quenching of the emissions in ambient solutions is discussed in terms of ligand labilization due to either thermal population of metal-centered excited states or direct labilization in the MLCT excited state due to enhanced trans effects of the Ir-C bonds on the Ir-S bonding.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic00079a005