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}]_nX_n (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}]_nX_n have been studied by NMR diffusion spectroscopy and dynamic light scattering measurements.