The functionalization of single-walled carbon nanotubes (SWCNTs) with luminescent sp3 defects has greatly improved their performance in applications such as quantum light sources and bioimaging. Here, we report the covalent functionalization of purified semiconducting SWCNTs with stable organic radicals (perchlorotriphenylmethyl, PTM) carrying a net spin.
This model system allows us to use the near-infrared photoluminescence arising from the defect-localized exciton as a highly sensitive probe for the short-range interaction between the PTM radical and the SWCNT. Our results point toward an increased triplet exciton population due to radical-enhanced intersystem crossing, which could provide access to the elusive triplet manifold in SWCNTs. Furthermore, this simple synthetic route to spin-labeled defects could enable magnetic resonance studies complementary to in vivo fluorescence imaging with functionalized SWCNTs and facilitate the scalable fabrication of spintronic devices with magnetically switchable charge transport.
Tuneable and low cost molecular electronics
Interaction of Luminescent Defects in Carbon Nanotubes with Covalently Attached Stable Organic Radicals
Felix J. Berger, J. Alejandro de SousaJ. Alejandro de Sousa, Shen Zhao, Nicolas F. Zorn, Abdurrahman Ali El Yumin, Aleix Quintana García, Simon Settele, Alexander Högele, Núria Crivillers, and Jana Zaumseil*
Since the inception of the atomic force microscope (AFM), dynamic methods (dynamic atomic force microscopy) have been very fruitful by establishing methods to quantify dissipative and conservative forces in the nanoscale and by providing a means to apply gentle forces to the samples with high resolution. Here, we discuss developments that cover over a decade of our work on energy dissipation, phase contrast, and the extraction of relevant material properties from observables.
Nickel(II) bis(dithiolene) complexes can provide crystalline conducting materials either in their monoanionic or neutral forms. Here we show that the use of chiral dithiolene ligands with one or two stereogenic centres, together with variation of the counter-ion in the anionic complexes, represents a powerful strategy to modulate the conducting properties of such molecular materials.The chiral ligands 5-methyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (me-dddt) and 5,6-dimethyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (dm-dddt) have been generated from the thione precursors 1 and 2 which have been structurally and chiroptically characterized.
The spin–spin interactions between unpaired electrons in organic (poly)radicals, especially nitroxides, are largely investigated and are of crucial importance for their applications in areas such as organic magnetism, molecular charge transfer, or multiple spin labeling in structural biology. Recently, 2,2,6,6-tetramethylpiperidinyloxyl and polymers functionalized with nitroxides have been described as successful redox mediators in several electrochemical applications; however, the study of spin–spin interaction effect in such an area is absent.
Metallacarboranes with the shape of the Greek letter θ, such as [Co(C2B9H11)2]−, were tested, for the first time, as efficient photoredox catalysts in the oxidation of aromatic and aliphatic alcohols in water. Their efficiency is linked to their high solubility in water, their high oxidizing power (Co4+/3+), and their absence of fluorescence on excitation, among others.
Resistive switching effect is observed for a gallium–indium/gallium oxide/graphene junction. The use of a gallium-based liquid metal (LM) alloy, in this case, the eutectic gallium–indium with its native gallium oxide skin, directly provides the metal top contact and the oxide layer needed to fabricate a memory.