A Tetrairon Dication Featuring Tetraethynylbenzene Bridging Ligand: A Molecular Prototype of Quantum Dot Cellular Automata

The unprecedented tetrairon dication [{Cp*(dppe)FeC≡C-}₄-μ-(1,2,4,5-C₆H₂)](PF₆)₂ ( 1 ) was obtained through a sequence of three reactions from 1,2,4,5-tetraethynylbenzene, Cp*(dppe)FeCl (Cp*=C₅Me₅, dppe=1,2-bis(diphenylphosphino)-ethane), KOtBu, and ferrocenium hexafluorophosphate. The cyclic voltammogram of the target molecule, isolated in 77 % yield, exhibits four well separated and reversible redox events showing that 1 is thermodynamically stable with respect to disproportionation (Kc>10⁶). The tetranuclear dication 1 was characterized by XRD on single crystal, IR and NMR spectroscopies and Mössbauer spectrometry. The experimental data show that 1 behaves as a class II mixed-valence complex with the positive charges preferentially disposed on antipodal positions. This new molecule can be regarded as a potential molecular prototype of quantum dot cellular automata.