Covalent Functionalization of Single-Walled Carbon Nanotubes by the Bingel Reaction for Building Charge-Transfer Complexes

Functionalization of nanotubes with donor and acceptor partners by the Bingel reaction leads to the formation of charge-transfer dyads, which can operate in organic photovoltaic devices. In this work, we theoretically examine the mechanism of the Bingel reaction for the (6,5)-chiral, (5,5)-armchair, and (9,0)-zigzag single-walled carbon nanotubes (SWCNTs), and demonstrate that the reaction is regioselective and takes place at the perpendicular position of (6,5)- and (5,5)-SWCNTs, and the oblique position of (9,0)-SWCNT. Further, we design computationally the donor–acceptor complexes based on (6,5)-SWCNT coupled with partners of different electronic nature. Analysis of their excited states reveals that efficient photoinduced charge transfer can be achieved in the complexes with π-extended analogue of tetrathiafulvalene (exTTF), zinc tetraphenylporphyrin (ZnTPP), and tetracyanoanthraquinodimethane (TCAQ). The solvent can significantly affect the population of the charge-separated states. Our calculations show that electron transfer (ET) occurs in the normal Marcus regime on a sub-nanosecond time scale in the complexes with exTTF and ZnTPP, and in the inverted Marcus regime on a picosecond time scale in the case of the TCAQ derivative. The ET rate is found to be not very sensitive to the degree of functionalization of the nanotube.