Article

Photophysical and theoretical studies on luminescent tetranuclear coinage metals building blocks

Organometallics 01/2006; 25:3639-3646.

ABSTRACT The synthesis, structural characterization, and the study of the photophysical properties of complexes
[Au2Ag2(C6F5)4(NtCCH3)2]n (1) and [Au2Cu2(C6F5)4(NtCCH3)2]n (2) have been carried out. The crystal
structure of both complexes consists of polymeric chains formed by repetition of Au2Ag2 or Au2Cu2
units built up by metallophilic Au(I)âââM(I) interactions that are linked through Au(I)âââAu(I) interactions.
Complexes 1 and 2 are brightly luminescent in the solid state at room temperature and at 77 K with
lifetimes in the nanosecond range. Both compounds 1 and 2 undergo oligomerization in solution, as
observed through UV-vis and excitation spectra in acetonitrile solutions at high concentrations. Thus,
a correlation between the excitation spectra in solution at different concentrations and the absorption
spectra in the solid state for complex 1 can be established. Time-dependent DFT calculations agree well
with the experimental results and support the idea of that the origin of the luminescence of these complexes
arises from orbitals located in the tetranuclear Au2M2 units.

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