Donor–Acceptor C 60 ‐Containing Polyferrocenylsilanes: Synthesis, Characterization, and Applications in Photodiode Devices

A series of polyferrocenylsilane (PFS) random copolymers containing covalently bound pendant [C 60 ]fullerene groups, the first well‐characterized metallopolymers with pendant C 60 units, have been prepared and characterized. The fullerene content of the prepared copolymers ranges from 7 to 24% relative to monomer unit. The desired copolymers were synthesized in three steps: metal‐catalyzed ring opening polymerization of sila[1]ferrocenophanes was performed to synthesize random copolymers of poly(ferrocenylmethylphenylsilane ‐co‐ ferrocenylchloromethylsilane); the resulting random PFSs were then functionalized by reaction with 11‐azido‐1‐undecanol to give PFSs with pendant azide groups; the desired donor–acceptor C 60 ‐containing PFSs were then synthesized by the reaction of the azide group in the side chains with C 60 in toluene at 110 °C. The resulting C 60 ‐containing PFSs are air‐stable and soluble in aromatic solvents, chloroform, or THF. The UV‐vis spectra of these materials show broad absorption up to 800 nm. Thin films of these materials were examined as the active layer in rare examples of all solid‐state sandwich‐type diode devices based on ferrocene‐fullerene dyads. The devices exhibit photoconducting and photovoltaic responses, with an open circuit potential of ca. 0.3 V under white light illumination.