Zusammenfassung
Complexes of the type Cu-I(tripod)X [tripod =1,1,1-tris(diphenylphosphanylmethyl)ethane; X- = Br-, I-, PhS-, PhC C-] are phosphorescent in solution and in the solid state (lambda(max) approximate to 465 nm). Calculations show that the emissive triplet is of mixed MLCT/LLCT character. The emission is facilitated by the rigid tetrahedral structure, which is imposed by the tripod ligand. ...
Zusammenfassung
Complexes of the type Cu-I(tripod)X [tripod =1,1,1-tris(diphenylphosphanylmethyl)ethane; X- = Br-, I-, PhS-, PhC C-] are phosphorescent in solution and in the solid state (lambda(max) approximate to 465 nm). Calculations show that the emissive triplet is of mixed MLCT/LLCT character. The emission is facilitated by the rigid tetrahedral structure, which is imposed by the tripod ligand. Accordingly, a distortion towards a square-planar geometry, which should occur upon MLCT excitation, is prevented. On the other hand, in the triplet state the phenyl substituents of the phosphane ligands undergo a rotation which favours radiationless deactivation. As a result, the emission efficiency is relatively small in solution, but much higher in the solid state owing to the rigidity of the lattice. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
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