Voltammetric studies on the inter-relationship between the redox chemistry of TTF, TTF+˙, TTF2+ and HTTF+ in acidic media

Adeel, Shahid; Abdelhamid, Muhammad E.; Nafady, Ayman; Li, Qi; Martin, Lisandra L.; Bond, Alan M.

doi:10.1039/c4ra16588h

Cited by 13 publications

(10 citation statements)

References 26 publications

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“…Bipolarons are suspected to be one of the causes of bias stress . Acid doping occurs for TTF and gives rise to a radical cation and a neutral radical that can eventually react further . Radical cations tend to react with water molecules to afford protons, hydroxyl radicals, and oxidized products that can further react with dioxygen .…”

Section: Charge Transportmentioning

confidence: 99%

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

et al. 2020

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The field of organic electronics has been prolific in the last couple of years, leading to the design and synthesis of several molecular semiconductors presenting a mobility in excess of 10 cm2 V−1 s−1. However, it is also started to recently falter, as a result of doubtful mobility extractions and reduced industrial interest. This critical review addresses the community of chemists and materials scientists to share with it a critical analysis of the best performing molecular semiconductors and of the inherent charge transport physics that takes place in them. The goal is to inspire chemists and materials scientists and to give them hope that the field of molecular semiconductors for logic operations is not engaged into a dead end. To the contrary, it offers plenty of research opportunities in materials chemistry.

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Section: Charge Transportmentioning

confidence: 99%

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

et al. 2020

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“…2). 9 A range of other MOFs have also been interrogated using spectroelectrochemical methods, particularly those incorporating the TTF functionality, an organosulfur moiety that undergoes two reversible one electron oxidations localised on separate rings, 84,85 and NDI, a wellstudied electron acceptor. 86 In the case of TTF, a partially oxidised ring has been shown to vastly improve conductivity, 87 while functionalised versions of NDI often display unique electronic, electrochemical and optical properties.…”

Section: Probing Redox Activity In Mofsmentioning

confidence: 99%

Exploiting redox activity in metal–organic frameworks: concepts, trends and perspectives

2016

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Of the many thousands of new metal-organic frameworks (MOFs) that are now discovered each year, many possess potential redox activity arising from the constituent metal ions and/or organic ligands, or the guest molecules located within their porous structures. Those redox states that can be accessed via postsynthetic redox modulation often possess distinct physical properties; if harnessed, these provide a basis for applications including microporous conductors, electrocatalysts, energy storage devices and electrochemical sensors, amongst others. This feature article highlights the latest developments in experimental, theoretical and computational concepts relevant to redox-active MOFs, including new solid state electrochemical and spectroelectrochemical techniques that have great utility in this field. A particular emphasis is on current and emerging trends at the fundamental level which underscore the importance of this promising class of electroactive materials for a wide range of technologically- and industrially-relevant applications.

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“…Two control experiments were conducted: (i) TTF and TA in the absence of Pt and under illumination, (ii) TTF and TA in the presence of Pt, without illumination. The UV–vis absorption spectra of these controls (Section SI2, Figure SI5a and b) show the disappearance of HTTF + and the gradual appearance of signals centered at 335, 436, and 582 nm, corresponding to TTF •+ . , However, H 2 was not detected, indicating that in the controls the oxidation of TTF is triggered by the reaction between HTTF + and TTF (eq 2, Scheme ). − In contrast, the photochemical reaction between TTF and TA in the presence of Pt yielded both TTF •+ (Figure a) and H 2 (Figure b), indicating that the HER by HTTF + requires both illumination and Pt.…”

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confidence: 97%

“…The cyclic voltammogram (CV) of HTTF + before electrochemical recycling (Figure a, cell described in Scheme ) shows the same features reported by Adeel et al The reversibility of both TTF •+ /TTF and TTF 2+ /TTF •+ redox processes is dramatically affected by the protonation of TTF, with the appearance of an irreversible oxidation process at around 1.6 V vs SHE, associated to the oxidation of HTTF + . In contrast, the CV taken after 51 h of in situ electrochemical recycling of TTF and continuous photo-HER (Figure a) shows partial recovery of the TTF •+ /TTF and TTF 2+ /TTF •+ processes and an increase of the reduction currents, which is due to the consumption of protons.…”

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confidence: 99%

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Photosensitized Hydrogen Evolution on a Floating Electrocatalyst Coupled to Electrochemical Recycling

2018

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Photoexcited protonated tetrathiafulvalene (HTTF) was found to act as a photosensitizer, injecting electrons into Pt microparticles (floating electrocatalysts) to produce H and TTF in acidic acetonitrile. In addition, TTF was electrochemically reduced back to TTF on a carbon electrode, to be further protonated to continuously produce H photochemically. The onset potential for the electrochemical recycling of TTF on carbon was set at a potential 500 mV more positive than the potential required for the direct reduction of protons. HTTF showed no signs of decomposition after 51 h of continuous recycling and photoinduced production of H, proving stability and reversibility.

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Voltammetric studies on the inter-relationship between the redox chemistry of TTF, TTF⁺˙, TTF²⁺ and HTTF⁺ in acidic media

Abstract: The chemistry of oxidized forms of TTF in acidified CH3CN has been established using electrochemical and spectroscopic techniques.

Cited by 13 publications

References 26 publications

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

Exploiting redox activity in metal–organic frameworks: concepts, trends and perspectives

Photosensitized Hydrogen Evolution on a Floating Electrocatalyst Coupled to Electrochemical Recycling

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