Assembly of Heterometallic Rigid-Rod Complexes and Coordination Oligomers from Gold(I) Metalloligands

The reactions of TpylC6­H4CCAuL (Tpyl = 2,2′:6′,2″-terpyridin-4′-yl; L = PPh3, CNXy; Xy = 2,6-dimethylphenyl) with MX2·nH2O (M = Fe, X = ClO4; M = Co, X = BF4; M = Zn, X = TfO, ClO4) in a 2:1 molar ratio give complexes [M­(Tpyl­C6H4­CC­AuL)2]­X2. Similarly, the reactions of PPN­[(TpylC6H4­CC)2Au] (PPN = (Ph3P)2N) with an equimolar amount of MX2·nH2O give coordination oligomers [M­{(TpylC6H4­CC)2­Au}]nXn (M = Fe, Zn, X = ClO4; M = Co, X = BF4). The complexes and oligomers have been isolated and characterized. The crystal structures of [Fe­(Tpyl­C6H4­CC­AuCNXy)2]­(ClO4)2 and [Co­(Tpyl­C6H4­CC­AuPPh3)2]­(BF4)2 have been determined by X-ray diffraction. The hydrodynamic sizes of complexes [M­(Tpyl­C6H4­CC­AuPPh3)2]­X2 and coordination oligomers [M­{(Tpyl­C6H4­CC)2­Au}]nXn have been studied by NMR diffusion spectroscopy and dynamic light scattering measurements.