Publication Date

8-2021

Date of Final Oral Examination (Defense)

6-17-2021

Type of Culminating Activity

Thesis

Degree Title

Master of Science in Chemistry

Department

Chemistry

Supervisory Committee Chair

Adam C. Colson, Ph.D.

Supervisory Committee Member

Eric Brown, Ph.D.

Supervisory Committee Member

Matthew King, Ph.D.

Abstract

Metal carbonyl clusters, such as the [Ni32C6(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 Fe2(μ-PPh2)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 Fe2(μ-PPh2)2(CO)6 redox mediators to arylisocyanide ligands. Specifically, the coordination of three Fe2(μ-PPh2)2(CO)6 subunits to a trifunctional arylisocyanide ligand produces an electron-sink ensemble that can accommodate six electrons, exceeding the precedent benchmark [Ni32C6(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.

DOI

https://doi.org/10.18122/td.1877.boisestate

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