Tuning the Carbon Nanotube Selectivity: Optimizing Reduction Potentials and Distortion Angles in Perylenediimides

Abstract

Different water-soluble perylenediimides (PDIs) have been used to individualize and stabilize single-walled carbon nanotubes (SWCNTs) in aqueous media. A key feature of the PDIs is that they can be substituted at the bay positions via the addition of two and/or four bromines. This enables control over structural and electronic PDI characteristics, which prompted us to conduct comparative assays with focus on SWCNTs' chirality and charge transfer. Electrochemical, microscopic, and spectroscopic experiments were used to investigate the SWCNT chiral selectivity of PDIs, on the one hand, and charge-transfer reactions between SWCNTs and PDIs, on the other hand.

The Green Box: An Electronically Versatile Perylene Diimide Macrocyclic Host for Fullerenes

“…The novel ground and excited state electronic interactions between the macrocycle's PDI components and potential pristine C60/70 fullerene guest species were therefore pursued and demonstrated via a non-covalent approach. 86 We have employed a range of techniques to comprehensively characterise the fullerene recognition properties of Green Box, 4, and its subsequent impact on the electronics of host and guest. For the first time, this work reveals a fullerene-based dyad with solvent tuneable partial charge ( [4] δ+ ⊂[C60] δ− ) or full electron transfer ([4] •+ ⊂[C60] •− ) in the ground state of the supramolecular complex assembly (Figure 1).…”

Amphiphilic Zinc Porphyrin Single‐Walled Carbon Nanotube Hybrids: Efficient Formation and Excited State Charge Transfer Studies

“…Recently, a myriad of studies regarding the photophysical/charge-transfer characteristics of SWCNTs with different molecular building blocks were reported. [8][9][10][11][12][13][14] Of significance is the fact that SWCNT hybrids have already found their way into device architectures, thereby passing the first step on the roadmap to real devices. [15] Chlorophyll is the active material in plants that absorbs sunlight and takes part in the electron transfer chain; a molecular roadway, through which the energy of photons is transferred by electrons.…”

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

“…3,4,5,6 To date, a number of donor-acceptor SWCNT-based hybrids are known, particularly, with porphyrins, ferrocenes, perylene diimides, phthalocyanines, and polyaromatic hydrocarbons. 7,8,9,10,11,12 Photoactive molecules can be attached to the nanotube via covalent or noncovalent interactions. Noncovalent functionalization preserves π-electron conjugation of the sp 2 carbon network but it is difficult to provide environmental and long-time stability of systems.In turn, covalent binding is strong, but usually generates sp 3 carbon sites on CNTs, which disrupt the transitions of π-electrons, leading to loss of desired properties.Insolubility of nanotubes and low charge mobility between donor and acceptor parts can be overcome by functionalization of nanotubes using Bingel cycloaddition reaction.…”

“…3,4,5,6 To date, a number of donor-acceptor SWCNT-based hybrids are known, particularly, with porphyrins, ferrocenes, perylene diimides, phthalocyanines, and polyaromatic hydrocarbons. 7,8,9,10,11,12 Photoactive molecules can be attached to the nanotube via covalent or noncovalent interactions. Noncovalent functionalization preserves π-electron conjugation of the sp 2 carbon network but it is difficult to provide environmental and long-time stability of systems.…”