How to Control the Rate of Heterogeneous Electron Transfer across the Rim of M <sub>6</sub> L <sub>12</sub> and M <sub>12</sub> L <sub>24</sub> Nanospheres
Riccardo Zaffaroni, Eduard O. Bobylev, Raoul Plessius, Jarl Ivar van der Vlugt, Joost N. H. Reek
Abstract
(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 nonconjugated) 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 electroactive catalysts and electrocatalytic applications of such supramolecular assemblies.