F. Neve, A. Crispini, S. Campagna
Apr 24, 1999
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Inorganic Chemistry
Abstract
The new functionalized polypyridine ligands 4‘-(4-chlorophenyl)-6‘-phenyl-2,2‘-bipyridine (clpbpy), 4‘-(4-tolyl)-6‘-phenyl-2,2‘-bipyridine (tpbpy), and 4‘-(4-carboxyphenyl)-6‘-phenyl-2,2‘-bipyridine (cpbpy), together with the known 4‘-(4-hydroxyphenyl)-6‘-phenyl-2,2‘-bipyridine (hpbpy) and 4‘-(4-tolyl)-2,2‘:6‘,2‘ ‘-terpyridine (ttpy) have been used to prepare a new series of Ir(III) cyclometalated compounds [Ir(ppy)2(HL-X)][PF6] (ppy is the monoanion of 2-phenylpyridine; HL-X = hpbpy (1), clpbpy (2), tpbpy (3), cpbpy (4), and ttpy (5)). All the new species have been characterized by IR and 1H NMR, and the crystal structure of 4 is also presented and discussed. All the metal complexes exhibit oxidation mainly centered on an orbital derived from an Ir−(C-) σ-bond and ligand-centered reduction processes; all of them are luminescent from 3MLCT levels both at 77 K in a rigid matrix and at 298 K in fluid solution. The redox and absorption properties are more or less insensitive to the remote substituents on the...