Electrochemically Mediated Au–C(sp2) Anchors for Molecular Electronics

Samajdar, Rajarshi; Yang, Hao; Yi, Seungjoo; Wang, Chun-I.; Putnam, Seth T.; Pence, Michael A.; Lindsay, Gavin S.; Meigooni, Moeen; Liu, Xiaolin; Ren, Jitong; Moore, Jeffrey S.; Tajkhorshid, Emad; Gewirth, Andrew A.; Rodríguez-López, Joaquín; Jackson, Nicholas E.; Schroeder, Charles M.

doi:10.1021/acs.jpcc.5c06124

Electrochemically Mediated Au–C(sp²) Anchors for Molecular Electronics

Journal Article · Fri Sep 19 04:00:00 EDT 2025 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5c06124· OSTI ID:3009739

Samajdar, Rajarshi ^[1]; Yang, Hao ^[1]; Yi, Seungjoo ^[1]; Wang, Chun-I. ^[1]; ^[1]; ^[1]; Lindsay, Gavin S. ^[1]; Meigooni, Moeen ^[1]; ^[1]; Ren, Jitong ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Univ. of Illinois at Urbana-Champaign, IL (United States)

Terminal anchor groups play a key role in the stability and electronic properties of molecular junctions. Single molecule junctions typically consist of two preinstalled terminal anchors linking organic molecules to metal electrodes. Here, in this work, we show that p-terphenyl derivatives containing only a single terminal anchor show conductance features similar to junctions with two preinstalled terminal anchors. A set of p-terphenyl derivatives with one terminal anchor was prepared using automated chemical synthesis and characterized using single molecule electronics experiments, molecular dynamics (MD) simulations, bulk electrochemistry and spectroscopy, and nonequilibrium Green’s function-density functional theory (NEGF-DFT) calculations. Our results show that 4-amino-p-terphenyl (PPP) and related analogs exhibit a well-defined high conductance state that is diminished or absent in other p-terphenyl derivatives lacking a preinstalled amine terminal anchor or fluorine or methyl substitutions at the terminal para position. However, a low conductance state is observed in all amino-p-terphenyl derivatives with one preinstalled anchor due to molecular junctions formed by noncovalent dimeric π–π stacking interactions. The observed high conductance state diminishes upon the addition of reducing agents and is restored upon the addition of an oxidizing agent. Our results suggest that the high conductance state arises due to Au–C(sp²) bond formation facilitated by a single electron oxidation event at the electrode surface. A series of control experiments with different anchor groups shows that primary amines play a key role in forming Au–C bonds for molecular junctions. Overall, these results suggest that Au–C bond formation gives rise to high conductance pathways in organic molecules containing only one preinstalled terminal anchor. Insights from this work can be leveraged in the design of molecular electronic devices, particularly in understanding the mechanisms of molecular binding and junction formation.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022035

OSTI ID:: 3009739

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 39 Vol. 125; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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