Open AccessExploring Electron-Sink Behaviors of Molecular Assemblies
Author(s) -
Yume Mai
Publication year - 2021
Language(s) - English
Resource type - Dissertations/theses
DOI - 10.18122/td.1877.boisestate
Subject(s) - redox , electron transfer , electron , electrochemistry , mesoscopic physics , crystallography , chemistry , ion , atomic physics , chemical physics , materials science , electrode , inorganic chemistry , physics , condensed matter physics , quantum mechanics , organic chemistry
Metal carbonyl clusters, such as the [Ni 32 C 6 (CO) 36 ] 6- anion, have been documented to display electron-sink phenomena. However, such large clusters suffer from inefficient yields due to their demanding and unreliable synthesis routes. To approach this obstacle, we investigated the electrochemical properties of Fe 2 (μ-PPh 2 ) 2 (CO) 6 , an organometallic complex known to experience a reversible two-electron transfer process. In this work, we report a modular synthetic strategy for expanding the electron-sink capacity of molecular assemblies by installing Fe 2 (μ-PPh 2 ) 2 (CO) 6 redox mediators to arylisocyanide ligands. Specifically, the coordination of three Fe 2 (μ-PPh 2 ) 2 (CO) 6 subunits to a trifunctional arylisocyanide ligand produces an electron-sink ensemble that can accommodate six electrons, exceeding the precedent benchmark [Ni 32 C 6 (CO) 36 ] 6- anion. The redox mediators store electrons within quantized unoccupied frontier orbitals and act as individual quantum capacitors. Ultimately, we propose to modify the electrode surfaces with these redox mediators to examine the relationship between the electrode’s mesoscopic structure and its macroscopic capacitance.