Methyldisulfide groups enable the direct connection of air-stable metal bis(terpyridine) complexes to gold surfaces

Trang, Christina D. M.; Saal, Thomas; Inkpen, Michael S.

doi:10.1039/d3dt00955f

Cited by 2 publications

(12 citation statements)

References 45 publications

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Section: Synthesis and Electrochemical Characterizationmentioning

confidence: 99%

“…In a recent study, 20 we showed that the tpySS ligand can be utilized for the preparation of a new family of sulfur-functionalized redox-active MSS (M = Fe, Co, Zn) complexes. These compounds were found to be air-stable in solution for ≥7 days, in contrast to thiolfunctionalized analogues, 20,21 and capable of forming single-component SAMs on gold surfaces. Here we report that analogous RuSS-1 and RuSS complexes may also be synthesized from tpySS and RuCl2(DMSO)(tpy) following the method of Ziessel et al, 29 using reaction temperatures that do not exceed 60℃.…”

Section: Synthesis and Electrochemical Characterizationmentioning

confidence: 99%

“…For ease of comparison, solution and surface voltammograms for MSS (M = Fe, Co, Zn) are reproduced here from an earlier report. 20 Critically, we maintain the potential window above ~−1.4 V vs. the FcH/[FcH] + redox couple in voltametric studies of these complexes to avoid irreversible reduction of the disulfide group. 20 Within this window, which also lies positive of any anticipated gold-sulfur reductive desorption processes, 35 we observe reversible redox events for all complexes except ZnSS which is redox silent over this potential range.…”

Section: Synthesis and Electrochemical Characterizationmentioning

confidence: 99%

“…20 Critically, we maintain the potential window above ~−1.4 V vs. the FcH/[FcH] + redox couple in voltametric studies of these complexes to avoid irreversible reduction of the disulfide group. 20 Within this window, which also lies positive of any anticipated gold-sulfur reductive desorption processes, 35 we observe reversible redox events for all complexes except ZnSS which is redox silent over this potential range. These features are assigned to the respective M 2+/3+ couple through comparison to the well-studied solution voltammograms of the parent [M(tpy)2] 2+ complexes (SI, Figure S2a and Table S1).…”

Section: Synthesis and Electrochemical Characterizationmentioning

confidence: 99%

“…Accordingly, here we explore the properties of monolayers prepared using a recently introduced 20 family of air-stable metal bis(terpyridine) complexes, [M(tpySS)(tpyR)](PF6)2 (MSS; M = Fe, Co, Zn, Ru; tpySS = 4′-(methyldisulfide)-2,2′:6′,2″-terpyridine) and [Ru(tpySS)(tpy)](PF6)2 (RuSS-1; tpy = 2,2′:6′,2″-terpyridine) (Figure 1a). These comprise either two or one methyldisulfide group(s) for binding to gold, respectively.…”

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confidence: 99%

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Counterion loss from charged surface-bound complexes drives the formation of loosely packed monolayers

Trang,

Mora Perez,

Ran

et al. 2024

Preprint

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The functionality of multicomponent self-assembled monolayers (SAMs) can be severely diminished by the segregation of like components into nanoscale domains, a process that maximizes favorable short-range intermolecular interactions. Here, we explore the use of a modular family of sulfur-functionalized metal bis(terpyridine) complexes ([M(tpy-R)2]2+(PF6–)2) to prepare mixed SAMs, considering that the comparable structure, dimensions, and ionic composition of these species should render them interchangeable within the adsorbed surface layer. While surface voltammetry experiments show these SAMs do exhibit compositions representative of their assembly solutions, they also suggest, in line with previous reports, that adjacent complexes in the monolayer are separated by a gap of ~1 nm. Remarkably, X-ray photoelectron spectroscopy studies reveal no F 1s peak features that would confirm the proliferation of PF6− counterions on the surface. We propose that the loose packed structure of these SAMs results from the loss or exchange of PF6– counterions which introduces significant repulsive Coulomb interactions between the adsorbed 2+ charged complexes. The hypothesis is supported by an electrostatic model which indicates these complexes should form close packed SAMs if mobile counterions are present. First-principles calculations demonstrate that complex-counterion binding interactions are weakened by charge transfer to the gold substrate, suggesting this may play an important role in the formation of such low coverage SAMs. Together, this study raises important questions regarding the assembly, organization, and composition of charged SAMs, and highlights new opportunities in the design of multicomponent monolayer assemblies with free volume, for example, to facilitate surface-based reactions or support molecular switches.

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Section: Synthesis and Electrochemical Characterizationmentioning

confidence: 99%

Section: Synthesis and Electrochemical Characterizationmentioning

confidence: 99%

Section: Synthesis and Electrochemical Characterizationmentioning

confidence: 99%

Section: Synthesis and Electrochemical Characterizationmentioning

confidence: 99%

mentioning

confidence: 99%

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Counterion loss from charged surface-bound complexes drives the formation of loosely packed monolayers

Trang,

Mora Perez,

Ran

et al. 2024

Preprint

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Bis(2,6-di(pyridin-2-yl)pyridin-4-yl)-6,6′-(1,2-diselanediyl)dihexanoate

Popa,

Andelescu,

Badea

et al. 2023

Molbank

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The present paper describes the preparation and characterization of a new dinuclear ligand based on terpyridine featuring a diselenide unit. This new compound was synthesized in a two-step procedure that first involved the insertion of the diselenide moiety on a carboxylic acid and was followed by a Steglich esterification reaction between the biscarboxylic acid containing the diselenide unit and 2,6-di(pyridin-2-yl)pyridin-4-ol (tpyOH). The title compound was characterized via FT-IR, Raman, NMR (1D and 2D), and UV-Vis spectroscopies and elemental analysis. Emission properties were investigated.

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Methyldisulfide groups enable the direct connection of air-stable metal bis(terpyridine) complexes to gold surfaces

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)2](PF6)2 (M = Fe, Co,...

Cited by 2 publications

References 45 publications

Counterion loss from charged surface-bound complexes drives the formation of loosely packed monolayers

Counterion loss from charged surface-bound complexes drives the formation of loosely packed monolayers

Bis(2,6-di(pyridin-2-yl)pyridin-4-yl)-6,6′-(1,2-diselanediyl)dihexanoate

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