Organogold oligomers: exploiting iClick and aurophilic cluster formation to prepare solution stable Au-4 repeating units

摘要

A novel synthetic method to create gold based metallo-oligomers/polymers via the combination of inorganic click (iClick) with intermolecular aurophilic interactions is demonstrated. Complexes [PEt3Au](4)(mu-N3C2C6H5) (1) and [PPhMe2Au](4)(mu-N3C2C6H5) (2) and {[PEt3Au](4)[(mu-N3C2)(2)-9,9-dihexyl-9H-fluorene]}(n) (8) have been synthesized via iClick. The tetranuclear structures of 1 and 2, induced by aurophilic bonding, are confirmed in the solid state through single crystal X-ray diffraction experiments and in solution via variable temperature NMR spectroscopy. The extended 1D structure of 8 is constructed by aurophilic induced self-assembly. H-1 DOSY NMR analysis reveals that the aurophilic bonds in 1, 2, and 8 are retained in the solution phase. The degree of polymerization within complex 8 is temperature and concentration dependent, as determined by 1H DOSY NMR. Complex 8 is a rare example of a solution stable higher ordered structure linked by aurophilic interactions.