We have prepared digold(I) complexes with the rigid-backbone diphosphane ligands PhanePhos, xyl-PhanePhos, and Ph 2 -GemPhos. All complexes were characterized by singlecrystal X-ray diffraction, NMR, IR, Raman, and photoluminescence (PL) spectroscopy. [PhanePhos(AuCl) 2 ] and [Gem-Phos(AuCl) 2 ] show a very similar ligand scaffold, but different (aurophilic vs. nonaurophilic) intramolecular Au-Au distances. Absorption and PL spectra of both compounds are quite similar. Theoretical investigations reveal that the excited states are of different character (i.e., influenced by the Au-Au contacts). The respective transition energies, however, lie close to each other, thus resulting in similar experi-

Gold(I) complexes ligated by phosphines with N-heterocycles in the periphery were prepared. First the synthesis of the ligands N-(diphenylphosphino)-4-(pyridin-2-yl)pyrimidin-2-amine (Hpypya) and N-(diphenylphosphino)-4-phenylpyrimidin-2-amine (Hphpya) are reported. These two compounds together with the related but earlier published ligands 3-(2-(diphenylphosphino)phenyl)-1H-pyrazole (Hph3py) and 5-(4-(diphenylphosphino)phenyl)-1H-pyrazole (Hph5py) were reacted with [(tht)AuCl] and [Au(tht)2]ClO4 to give the heteroleptic complexes [(L)AuCl] and the homoleptic compounds [(L)2Au]ClO4 (L = Hpypya, Hphpya, Hph3py, and Hph5py). Single crystal X-ray diffraction studies revealed that the heteroleptic complexes form hydrogen bonds between two N-heterocycles of neighboring complexes resulting in dimeric structures. The homoleptic complexes show a different behavior.

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