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A new series of bis(ferrocenylethynyl) complexes, 3-7, and a mono(ferrocenylethynyl) complex, 8, have been synthesized incorporating conjugated heterocyclic spacer groups, with the ethynyl group facilitating an effective long-range intramolecular interaction. The complexes were characterized by NMR, IR, and UV-vis spectroscopy as well as X-ray crystallography. The redox properties of these complexes were investigated using cyclic voltammetry and spectroelectrochemistry. Although there is a large separation of ∼14 Å between the two redox centers, ΔE(1/2) values in this series of complexes ranged from 50 to 110 mV. The appearance of intervalance charge-transfer bands in the UV-vis-near-IR region for the monocationic complexes further confirmed effective intramolecular electronic communication. Computational studies are presented that show the degree of delocalization across the Fc-C≡C-C≡C-Fc (Fc = C5H5FeC5H4) highest occupied molecular orbital.

inorganic chemistry

Long-Range Intramolecular Electronic Communication in Bis(ferrocenylethynyl) Complexes Incorporating Conjugated Heterocyclic Spacers: Synthesis, Crystallography, and Electrochemistry