Issue 42, 2020

Transferrable property relationships between magnetic exchange coupling and molecular conductance

Abstract

Calculated conductance through Aun–S–Bridge–S–Aun (Bridge = organic σ/π-system) constructs are compared to experimentally-determined magnetic exchange coupling parameters in a series of TpCum,MeZnSQ–Bridge–NN complexes, where TpCum,Me = hydro-tris(3-cumenyl-1-methylpyrazolyl)borate ancillary ligand, Zn = diamagnetic zinc(II), SQ = semiquinone (S = 1/2), and NN = nitronylnitroxide radical (S = 1/2). We find that there is a nonlinear functional relationship between the biradical magnetic exchange coupling, JD→A, and the computed conductance, gmb. Although different bridge types (monomer vs. dimer) do not lie on the same JD→Avs. gmb, curve, there is a scale invariance between the monomeric and dimeric bridges which shows that the two data sets are related by a proportionate scaling of JD→A. For exchange and conductance mediated by a given bridge fragment, we find that the ratio of distance dependent decay constants for conductance (βg) and magnetic exchange coupling (βJ) does not equal unity, indicating that inherent differences in the tunneling energy gaps, Δε, and the bridge–bridge electronic coupling, HBB, are not directly transferrable properties as they relate to exchange and conductance. The results of these observations are described in valence bond terms, with resonance structure contributions to the ground state bridge wavefunction being different for SQ–Bridge–NN and Aun–S–Bridge–S–Aun systems.

Graphical abstract: Transferrable property relationships between magnetic exchange coupling and molecular conductance

Supplementary files

Article information

Article type
Edge Article
Submitted
07 8月 2020
Accepted
14 9月 2020
First published
08 10月 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 11425-11434

Transferrable property relationships between magnetic exchange coupling and molecular conductance

M. L. Kirk, R. Dangi, D. Habel-Rodriguez, J. Yang, D. A. Shultz and J. Zhang, Chem. Sci., 2020, 11, 11425 DOI: 10.1039/D0SC04350H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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