Connectivity-Dependent Conductance of 2,2'-Bipyridine-Based Metal Complexes.


Chelli, Yahia, Ferri, Nicolò, Vezzoli, Andrea ORCID: 0000-0002-8059-0113, Davidson, Ross J, Morris, James, Nichols, Richard J ORCID: 0000-0002-1446-8275, Higgins, Simon J ORCID: 0000-0003-3518-9061, Sangtarash, Sara, Sadeghi, Hatef, Yufit, Dmitry S et al (show 1 more authors) (2023) Connectivity-Dependent Conductance of 2,2'-Bipyridine-Based Metal Complexes. ACS omega, 8 (51). pp. 48958-48965.

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Abstract

The present work provides an insight into the effect of connectivity isomerization of metal-2,2'-bipyridine complexes. For that purpose, two new 2,2'-bipyridine (bpy) ligand systems, 4,4'-bis(4-(methylthio)phenyl)-2,2'-bipyridine (L<sup>meta</sup>) and 5,5'-bis(3,3-dimethyl-2,3-dihydrobenzothiophen-5-yl)-2,2'-bipyridine (L<sup>para</sup>) were synthesized and coordinated to rhenium and manganese to obtain the corresponding complexes MnL<sup>meta</sup>(CO)<sub>3</sub>Br, ReL<sup>meta</sup>(CO)<sub>3</sub>Br, MnL<sup>para</sup>(CO)<sub>3</sub>Br, MoL<sup>para</sup>(CO)<sub>4</sub> and ReL<sup>para</sup>(CO)<sub>3</sub>Br. The experimental and theoretical results revealed that coordination to the para system, i.e., the metal ion peripheral to the conductance path, gave a slightly increased conductance compared to the free ligand attributed to the reduced highest occupied molecular orbital (HOMO)-least unoccupied molecular orbital (LUMO) gap. The meta-based system formed a destructive quantum interference feature that reduced the conductance of a S···S contacted junction to below 10<sup>-5.5</sup><i>G</i><sub>o</sub>, reinforcing the importance of contact group connectivity for molecular wire conductance.

Item Type: Article
Divisions: Faculty of Science and Engineering > School of Physical Sciences
Depositing User: Symplectic Admin
Date Deposited: 30 Jan 2024 10:04
Last Modified: 30 Jan 2024 10:56
DOI: 10.1021/acsomega.3c06555
Open Access URL: https://doi.org/10.1021/acsomega.3c06555
Related URLs:
URI: https://livrepository.liverpool.ac.uk/id/eprint/3178077
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