Synthesis of Multifunctional Charge-Transfer Agents: Toward Single-Walled Carbon Nanotubes with Defined Covalent Functionality and Preserved π System

Abstract

The attachment of well-defined charge-transfer agents to the surface of nanomaterials is an efficient strategy to control their charge density and also to tune their optical, electrical, and physicochemical properties. Particularly interesting are charge-transfer agents that either donate or withdraw electrons depending on the arrangements of their building units and that promise a nondestructive attachment to delicate nanomaterials like sp2 compounds. In this work, we rationally synthesize molecular moieties with versatile functionalities. A reactive anchor group allows us to attach them to carbon nanotubes as defined charge-transfer agents while preserving the tubes’ π-conjugation. The charge-transfer agents were synthesized through the stepwise nucleophilic substitution of either one (monosubstituted series) or two (disubstituted series) chlorine atoms of cyanuric chloride by aniline derivatives containing one, two, or three methoxy groups in the para and meta positions. Variation in the number and position of the methoxy group as an electron-transferring group helps us to manipulate the electronic and optical properties of the molecular probes and their charge transfer to the single-walled carbon nanotubes (SWNTs) systematically. The correlation between the optical properties of these molecular probes and their functionality was investigated by experiments and quantum chemical calculations. While the optoelectronic properties of the conjugated charge-transfer agents were dominated by the aniline segments, the triazine warrants the ability to nondestructively attach to the surface of SWNTs. This study is one step ahead toward the production of SWNTs with desired optical and electrical properties by covalent π-preserving functionalization.