Quantum Interference in Atomic and Molecular Systems

The strategy of anchoring molecular catalysts on electrode surfaces combines the high selectivity and activity of molecular systems with the practicality of heterogeneous systems. The stability of molecular catalysts is, however, far less than that of traditional heterogeneous electrocatalysts, and therefore a method to easily replace anchored molecular catalysts that have degraded could make such electrosynthetic systems more attractive. Here, we apply a non-covalent “click” chemistry approach to reversibly bind molecular electrocatalysts to electrode surfaces via host-guest complexation with surface-anchored cyclodextrins. The host-guest interaction is remarkably strong and allows the flow of electrons between the electrode and the guest catalyst. Electrosynthesis in both organic and aqueous media was demonstrated on metal oxide electrodes, with stability on the order of hours. The catalytic surfaces can be recycled by controlled release of the guest from the host cavities and readsorption of fresh guest. This strategy represents a new approach to practical molecular-based catalytic systems.

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Mechanically-Tunable Quantum Interference in Ferrocene-Based Single-Molecule Junctions

10.26434/chemrxiv.12252059 ◽

2020 ◽

Author(s):

María Camarasa-Gómez ◽

Daniel Hernangómez-Pérez ◽

Michael S. Inkpen ◽

Giacomo Lovat ◽

E-Dean Fung ◽

...

Keyword(s):

Single Molecule ◽

Quantum Interference ◽

Degrees Of Freedom ◽

Building Blocks ◽

Ferrocene Derivative ◽

Single Molecule Junctions ◽

Molecule Junction ◽

Single Molecule Junction ◽

The Impact ◽

D Orbitals

Ferrocenes are ubiquitous organometallic building blocks that comprise a Fe atom sandwiched between two cyclopentadienyl (Cp) rings that rotate freely at room temperature. Of widespread interest in fundamental studies and real-world applications, they have also attracted some interest as functional elements of molecular-scale devices. Here we investigate the impact of the configurational degrees of freedom of a ferrocene derivative on its single-molecule junction conductance. Measurements indicate that the conductance of the ferrocene derivative, which is suppressed by two orders of magnitude as compared to a fully conjugated analog, can be modulated by altering the junction configuration. Ab initio transport calculations show that the low conductance is a consequence of destructive quantum interference effects that arise from the hybridization of metal-based d-orbitals and the ligand-based π-system. By rotating the Cp rings, the hybridization, and thus the quantum interference, can be mechanically controlled, resulting in a conductance modulation that is seen experimentally.

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