Donor–Acceptor C₆₀‐Containing Polyferrocenylsilanes: Synthesis, Characterization, and Applications in Photodiode Devices

Abstract

A series of polyferrocenylsilane (PFS) random copolymers containing covalently bound pendant [C60]fullerene groups, the first well‐characterized metallopolymers with pendant C60 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 C60‐containing PFSs were then synthesized by the reaction of the azide group in the side chains with C60 in toluene at 110 °C. The resulting C60‐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.

Optical and Luminescence Properties and Applications of Metal Complex‐Based Polymers

“…0.3 to 0.45 V [95]. Similar responses were obtained when the fullerenes were covalently attached to the polysilane backbone [96]. …”

Harvesting solar energy using conjugated metallopolyyne donors containing electron-rich phenothiazine–oligothiophene moieties

“…Among these, metallpolyynes stand out to be particularly interesting candidates in this area [23][24][25][26][27][28][29][30][31][32][33][34][35][36]. For a rational design of solar cells with the aim of optimizing solar spectrum coverage and charge mobility, both in single and tandem cells, it is very desirable to seek for a new class of conjugated polymers with tunable functional properties for PSCs so that they can be processed under similar conditions and the cell design and optimization processes can be simplified [48][49][50][51][52][53][54][55]. It has been shown that organic groups such as fluorene [35], 2,1,3-benzothiadiazole [31,34], thieno [3,4-b]pyrazine [36] and bithiazole [32] can be used to prepare efficient organometallic PSCs with the photosensitivity at longer wavelengths due to their narrow bandgaps.…”

Buckyballs

“…In the present section, some of the most promising and recent applications for C 60 -polymers will be shown. Since 1991 fullerene polymers have been studied as active materials in membranes both for gas separation [91,92] and for proton exchange fuel cells [93], and also as active polymers in electroluminescent devices [77,94,95] and in non-volatile flash devices [96], among others. One of the most promising applications for polyfullerenes seems to be as an active layer in optical limiters.…”