Triphenylphosphine Oxide: A Versatile Covalent Functionality for Carbon Nanotubes.

Broadening the scope of functionalities that can be covalently bound to single-walled carbon nanotubes (SWCNTs) is crucial for enhancing the versatility of this promising nanomaterial class in applied settings. Here we report the covalent linkage of triphenylphosphine oxide [Ph3P(O)] to SWCNTs, a hitherto overlooked surface functionality. We detail the synthesis and structural characterization of a new family of phosphine oxide-functionalized diaryliodonium salts that can facilitate direct Ph3P(O) transfer and afford novel SWCNTs with tunable Ph3P(O) content (SWCNT-P). The molecularly-distributed and robust nature of the covalent Ph3P(O) attachment in SWCNT-P was supported by a combination of characterization methods including Raman, infrared, UV-Vis-NIR and X-ray photoelectron spectroscopies coupled with thermogravimetric analysis. Electron microscopy further revealed the effectiveness of the Ph3P(O) moiety for de-bundling SWCNTs to yield SWCNT-P with superior dispersibility and processability. Finally, electrochemical studies established that SWCNT-P is sensitive to the presence of Li+, Na+ and K+ wherein the Gutmann-Beckett Lewis acidity parameters of the ions were quantitatively transduced by Ph3P(O) to electrochemical responses. This work hence presents a synthetic, structural, spectroscopic and electrochemical foundation for a new phosphorus-enriched responsive nanomaterial platform featuring the Ph3P(O) functionality.

A Dye-Sensitized Sensor for Oxygen Detection under Visible Light.

Sensors that can accurately assess oxygen (O2) concentrations in real time are crucial for a wide range of applications spanning personal health monitoring, environmental protection, and industrial process development. Here a high-performance chemiresistive sensor that allows for the rapid detection of O2 at room temperature under visible light illumination is described. Inspired by the operating principles of dye-sensitized solar cells, the chemiresistor is based on a single-walled carbon nanotube-titania hybrid (SWCNT-TiO2) bearing a molecular Re-based photosensitizer [(Pbpy)(CO)3ReBr] (Pbpy = 4,4'-[P(O)(OH)2]2-2,2'-bipyridine). The resulting SWCNT-TiO2-Re composite undergoes photoinduced charge transfer that is sensitive to ppb levels of O2, thereby yielding a rapid and reversible chemiresistive response. Owing to its unique mode of operation and robust components, the sensor shows a high degree of selectivity for O2 over a range of interferants, humidity tolerance, and multimonth benchtop stability. The approach presented herein demonstrates the translatability of concepts in light harvesting to the development of robust, rapid, and low-power sensing technologies.

Phosphine Oxide-Functionalized Terthiophene Redox Systems.

Main group systems capable of undergoing controlled redox events at extreme potentials are elusive yet highly desirable for a range of organic electronics applications including use as energy storage media. Herein we describe phosphine oxide-functionalized terthiophenes that exhibit two reversible 1e- reductions at potentials below -2 V vs Fc/Fc+ (Fc=ferrocene) while retaining high degrees of stability. A phosphine oxide-functionalized terthiophene radical anion was synthesized in which the redox-responsive nature of the platform was established using combined structural, spectroscopic, and computational characterization. Straightforward structural modification led to the identification of a derivative that exhibits exceptional stability during bulk 2 e- galvanostatic charge-discharge cycling and enabled characterization of a 2 e- redox series. A new multi-electron redox system class is hence disclosed that expands the electrochemical cell potential range achievable with main group electrolytes without compromising stability.

Asymmetric Hydrogenation of Aryl Perfluoroalkyl Ketones Catalyzed by Rhodium(III) Monohydride Complexes Bearing Josiphos Ligands.

The asymmetric hydrogenation of 2,2,2-trifluoroacetophenones and aryl perfluoroalkyl ketones was developed using a unique, well-defined chloride-bridged dinuclear rhodium(III) complex bearing Josiphos-type diphosphine ligands. These complexes were prepared from [RhCl(cod)]2 , Josiphos ligands, and hydrochloric acid. As catalyst precursors, they allow for the efficient and enantioselective synthesis (up to 99 % ee) of chiral secondary alcohols with perfluoroalkyl groups. This system does not require an activating base for the hydrogenation of 2,2,2-trifluoroacetophenones. Additionally, the enantioselective C=O hydrogenations of 2-phenyl-3-(haloacetyl)-indoles, a class of privileged structures in medicinal chemistry, is reported for the first time.