Ultrafast electron transfer in all-carbon-based SWCNT–C60 donor–acceptor nanoensembles connected by poly(phenylene–ethynylene) spacers

Abstract

Building all-carbon based functional materials for light energy harvesting applications could be a solution to tackle and reduce environmental carbon output. However, development of such all-carbon based donor–acceptor hybrids and demonstration of photoinduced charge separation in such nanohybrids is a challenge since in these hybrids part of the carbon material should act as an electron donating or accepting photosensitizer while the second part should fulfil the role of an electron acceptor or donor. In the present work, we have successfully addressed this issue by synthesizing covalently linked all-carbon-based donor–acceptor nanoensembles using single-walled carbon nanotubes (SWCNTs) as the donor and C₆₀ as the acceptor. The donor–acceptor entities in the nanoensembles were connected by phenylene–ethynylene spacer units to achieve better electronic communication and to vary the distance between the components. These novel SWCNT–C₆₀ nanoensembles have been characterized by a number of techniques, including TGA, FT-IR, Raman, AFM, absorbance and electrochemical methods. The moderate number of fullerene addends present on the side-walls of the nanotubes largely preserved the electronic structure of the nanotubes. The thermodynamic feasibility of charge separation in these nanoensembles was established using spectral and electrochemical data. Finally, occurrence of ultrafast electron transfer from the excited nanotubes in these donor–acceptor nanohybrids has been established by femtosecond transient absorption studies, signifying their utility in building light energy harvesting devices.