Single-molecule imaging and kinetic analysis of intermolecular polyoxometalate reactions

Abstract

We induce and study reactions of polyoxometalate (POM) molecules, [PW12O40]3− (Keggin) and [P2W18O62]6− (Wells–Dawson), at the single-molecule level, utilising TEM as an analytical tool, and nanotubes as test tubes.

Stabilization of Polyoxometalate Charge Carriers via Redox‐Driven Nanoconfinement in Single‐Walled Carbon Nanotubes

“…1 nm, though note that terminal oxygen are not typically observed with TEM). Similar to their polyoxotungstate analogues, [54] the discrete species appeared to rapidly condense to larger nanoparticles during TEM observations, indicating that O atoms had dissociated from the POMs under the electron beam (Figure S1). Raman spectroscopy of PMo 12 @SWNT also provided strong evidence for POM encapsulation.…”

Ionization and electron excitation of C 60 in a carbon nanotube: A variable temperature/voltage transmission electron microscopic study

“…Variable-temperature single-molecule atomic-resolution time-resolved electron microscopic (VT-SMART-EM) imaging is an emerging experimental tool for the study of kinetics and thermodynamics of individual chemical events ( 19 , 22 , 38 ), and it has provided direct experimental proof of the Rice–Ramsperger–Kassel–Marcus theory ( 39 ). In this study, we monitored several hundred individual events of the [2 + 2] reaction under VT/VV conditions at 103 to 493 K and 60 to 120 keV ( 10 , 19 ).…”

Polyoxometalate steric hindrance driven chirality-selective separation of subnanometer carbon nanotubes

“…These redox materials exhibit exceptional electrochemical stability. [70][71][72] We demonstrated that the formation of electron donor-acceptor systems composed of SWCNTs and encapsulated polyoxometalates is effective to modulate the interaction of inter-tubes, thus selectively extracting largediameter semiconducting SWCNTs. 73,74 The adaptability in chemical synthesis provides a wide variety of customized polyoxometalates with tunable redox potentials, which enables precise modulation of the electronic properties of SWCNTs.…”