A molecular cage {Au (μ-PAnP) [Fe(H O) (TPyP)] (OTf) }(OTf) (1) composed of two cofacial Fe -porphyrin can be self-assembled from the gold clip [Au (PAnP)Cl ] and Fe (H O) (TPyP) (PAnP=9,10-bis(diphenylphosphino)anthracene, TPyP=meso-tetra(4-pyridyl)porphyrinato). The height of the cage is 8.579(3) Å. The addition of a base to a solution of the cage leads to a contracted and twisted cage {[Au (μ-PAnP) [Fe (μ-O)(TPyP) ]}(OTf) (2), which has a height of ≈4.4 Å and porphyrin-porphyrin torsional angle of ≈20°. The contracted cage can be synthesized independently from the gold clip and Fe (μ-O)(TPyP) . The spectroscopy and crystal structure of an unclipped analog of the contracted cage, {[AuPPh ) [Fe (μ-O)(TPyP) ]}(OTf) (3), supports the DFT-calculated structure of 2. NMR and UV/Vis titrations show that the expansion-untwisting and contraction-twisting of the cage is reversible.

Heteroleptic and homoleptic binuclear Au(I) complexes [Au2(-PAnP)(SPh)(X)] (X = Cl or Br), [Au2(-PAnP)(SPh)2] and [Au2(-PAnP)(SPhCO2H)2] (SPh = benzenethiolate and SPhCO2H = 4-thiolatobenzoic acid) containing a bridging diphosphine, 9,10-bis(diphenylphosphino)anthracene (PAnP),...

A tetranuclear gold(I) complex [Au4(μ-PAnP)2(μ-L)2] (PAnP = 9,10-bis(diphenylphosphino)anthracene and L = benzene-1,2-dithiolate) has been synthesized and characterised by multinuclear NMR and X-ray crystallography. The molecule has a cyclophane-like structure...