Inner-Shell Effects on Heterogeneous Electron-Transfer Rates of Bis(1,4,7-Triazacyclononane) (tacn) Redox Couples, M(tacn)23+/2+ (M = Fe, Co, Ni, Ru)

1994 ◽  
Vol 33 (19) ◽  
pp. 4344-4350 ◽  
Author(s):  
Philip W. Crawford ◽  
Franklin A. Schultz
Keyword(s):  
Electron Transfer ◽  
Transfer Rates ◽  
Shell Effects ◽  
Heterogeneous Electron Transfer ◽  
Redox Couples

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

2020 ◽  
Author(s):  
Riccardo Zaffaroni ◽  
Eduard.O. Bobylev ◽  
Plessius, Raoul ◽  
Jarl Ivar van der Vlugt ◽  
Joost reek
Keyword(s):  
Electron Transfer ◽  
Active Species ◽  
Transition Metal Catalysts ◽  
Supramolecular Assemblies ◽  
Fine Tuning ◽  
Transfer Rates ◽  
Heterogeneous Electron Transfer ◽  
Redox Active ◽  
Kinetics Of ◽  
Fine Tune

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 M<sub>6</sub>L<sub>12 </sub>and larger M<sub>12</sub>L<sub>24</sub> (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.

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