A new series of dinuclear Au(I) complexes linked by diethynylpyridine groups

A series of novel digold complexes incorporating ethynyl pyridine derivatives as a spacer unit, (R(3)P)Au(Ctriple bond]C)X(Ctriple bond]C)Au(PR(3))] (R = Ph, X = 2,5-pyridine (1); R = Cy (cyclohexane), X = 2,5-pyridine (2); R = Ph, X = 2,6-pyridine (3); R = Ph, X = 2,5'-bipyridine (4); R = Ph, X = 2,6'-bipyridine (5)), has been synthesised. All the complexes have been characterised spectroscopically and the structures determined by single-crystal X-ray crystallography. The central (Ctriple bond]C)(X)(Ctriple bond]C) unit is essentially linear for complexes 1, 2 and 4 and kinked for complexes 3 and 5, but only in 1, with the shortest spacer group and the less bulky phosphine ligand, is there evidence of d(10)...d(10) Au...Au interactions (Au-Au 3.351(2) A). The solution UV/visible absorption and emission spectra for all the complexes are similar to those of the free ligands suggesting that the spectra are dominated by pi-pi* ligand-centred transitions and this is confirmed by DFT calculations.