How to Control the Rate of Heterogeneous Electron Transfer Across the Rim of M6L12 and M12L24 Nanospheres

17 February 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Catalysis in confined spaces, such as provided by supramolecular cages, is quickly gaining momentum. It allows for second coordination sphere strategies to control the selectivity and activity of transition metal catalysts, beyond the classical methods like fine-tuning the steric and electronic properties of the coordinating ligands. Only a few electrocatalytic reactions within cages have been reported, and there is no information regarding the electron transfer kinetics and thermodynamics of redox-active species encapsulated into supramolecular assemblies. This contribution revolves around the preparation of M6L12 and larger M12L24 (M= Pd or Pt) nanospheres functionalized with different numbers of redox-active probes encapsulated within their cavity, either in a covalent fashion via different types of linkers (flexible, rigid and conjugated or rigid and non-conjugated) or by supramolecular hydrogen bonding interactions. The redox-probes can be addressed by electrochemical electron transfer across the rim of nanospheres and the thermodynamics and kinetics of this process are described. Our study identifies that the linker type and the number of redox probes within the cage are useful handles to fine-tune the electron transfer rates, paving the way for the encapsulation of electro-active catalysts and electrocatalytic applications of such supramolecular assemblies.

Keywords

Self-assembly, Nanospheres, Electrochemistry, kinetics

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.