Methyldisulfide Groups Enable the Direct Connection of Air-stable Metal Bis(terpyridine) Complexes to Gold Surfaces

Overview

Journal Dalton Trans

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2023 May 23

PMID 37218422

Authors

Christina D M Trang

Thomas Saal

Michael S Inkpen

Affiliations

Soon will be listed here.

Abstract

We show that a new terpyridine ligand comprising a directly-connected methyldisulfide group (tpySSMe) can be used to prepare a modular series of metal bis(terpyidine) complexes, [M(tpySSMe)](PF) (M = Fe, Co, Zn), suitable for the functionalization of metal surfaces. Critically, we find these complexes are air-stable in solution for >7 d, in stark contrast to their thiol-substituted analogues, [M(tpySH)](PF) (M = Fe, Co), which decompose in <1 d. While CoSH has previously been utilized in several important studies, we explicitly detail its synthesis and characterization here for the first time. We subsequently probe the electrochemical properties of [M(tpySSMe)](PF) in solution, showing that the (electro)chemical reactions associated with disulfide reduction significantly increase the complexity of the voltammetric response. In preliminary surface voltammetry studies, we confirm that CoSS and FeSS form solution-stable self-assembled monolayers (SAMs) on gold with comparable electrochemical properties to those formed from CoSH. Taken together, this work provides a robust foundation for future studies of this prominent class of complexes as redox-active components of SAMs or single-molecule junctions.

Citing Articles

Counterion Loss from Charged Surface-Bound Complexes Drives the Formation of Loosely Packed Monolayers.

Trang C, Perez C, Ran J, Prezhdo O, Inkpen M J Am Chem Soc. 2024; 146(37):25625-25639.

PMID: 39250739 PMC: 11421008. DOI: 10.1021/jacs.4c07327.

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