Synthesis and characterisation of polymeric materials consisting of {Fe2(CO)5}-unit and their relevance to the diiron sub-unit of [FeFe]-hydrogenase.

By using "click" chemistry between a diazide and a diiron model complex armed with two alkynyl groups, two polymeric diiron complexes (Poly-Py and Poly-Ph) were prepared. The two polymeric complexes were investigated using infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), Mössbauer spectroscopy, and cyclic voltammetry (Poly-Py only, due to the insolubility of Poly-Ph). To probe the coordinating mode of the diiron units in the two polymeric complexes, two control complexes (3 and 4) were also synthesised using a monoazide. Complexes 3 and 4 were well characterised and the latter was further crystallographically analysed. It turns out that in both complexes (3 and 4) and the two polymeric diiron complexes, one of the two iron atoms in the diiron unit coordinates with one of the triazole N atoms. Our results revealed that both morphologies and properties of Poly-Py and Poly-Ph are significantly affected by the organic moiety of the diazide. Compared to the protonating behaviour of the complexes 3 and 4, Poly-Py exhibited proton resistance. In electrochemical reduction, potentials for the reduction of the diiron units in Poly-Py and hence its catalytic reduction of proton in acetic acid-DMF shifted by over 400 mV compared to those for complexes 3 and 4. It is likely that the polymeric nature of Poly-Py offers the diiron units a "protective" environment in an acidic medium and more positive reduction potential.