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Luminescence and Theoretical Studies of Cu(tripod)X [tripod = 1,1,1‐Tris(diphenylphosphanylmethyl)ethane; X – = Halide, Thiophenolate, Phenylacetylide]
Author(s) -
Pawlowski Valeri,
Knör Günther,
Lennartz Christian,
Vogler Arnd
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400959
Subject(s) - tripod (photography) , chemistry , phosphorescence , halide , luminescence , photochemistry , tetrahedron , tris , solid state , crystallography , fluorescence , inorganic chemistry , optoelectronics , optics , biochemistry , physics
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 ( λ max ≈ 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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)