Magnetic perturbation of the redox potentials of localized and delocalized mixed-valence complexes

Lapinte, Claude

doi:10.1016/j.jorganchem.2007.09.030

Cited by 98 publications

(88 citation statements)

References 65 publications

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“…Ferrocene units are only marginally better than TTFs, but the interaction can here also be increased by “doubly-bridging” them [13]. Those redox groups that have shown the best interaction along the all-carbon bridges are the organometallic metal centres Re(NO)(PPh 3 )Cp* [24], Ru(dppe)Cp* [25], and Fe(dppe)Cp* [26] (Cp* = 1,2,3,4,5- pentamethylcyclopentadienyl), showing good communication still well past five carbon–carbon triple bonds between the metal centres.…”

Section: Resultsmentioning

confidence: 99%

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

Jiang¹,

Mazzanti

Parker³

et al. 2015

Beilstein J. Org. Chem.

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SummaryA selection of cyclic and acyclic acetylenic scaffolds bearing two tetrathiafulvalene (TTF) units was prepared by different metal-catalyzed coupling reactions. The bridge separating the two TTF units was systematically changed from linearly conjugated ethyne, butadiyne and tetraethynylethene (trans-substituted) units to a cross-conjugated tetraethynylethene unit, placed in either acyclic or cyclic arrangements. The cyclic structures correspond to so-called radiaannulenes having both endo- and exocyclic double bonds. Interactions between two redox-active TTF units in these molecules were investigated by cyclic voltammetry, UV–vis–NIR and EPR absorption spectroscopical methods of the electrochemically generated oxidized species. The electron-accepting properties of the acetylenic cores were also investigated electrochemically.

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Section: Resultsmentioning

confidence: 99%

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

Jiang¹,

Mazzanti

Parker³

et al. 2015

Beilstein J. Org. Chem.

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“…Therefore, the introduction of aromatic rings such as thiophene or benzene {[Cp*(dppe)Fe–C≡C–(1,4‐C 6 H 4 )–C≡C–Fe(dppe)Cp*][PF 6 ] n ( 7 [PF 6 ] n ) ( n = 0–2) constitutes a well‐known example}9,10 in the polyynediyl spacer is an attractive alternative to circumvent this instability as well as to tune the physical properties of the assemblies 9,11,12. Consequently, the various new nonlinear geometries that can be envisioned for different carbon‐rich spacers lead to structural variation, which can deeply modify the electronic and magnetic properties of the molecules both in the bulk and at the single‐molecule level 5,7,13…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of a Mixed‐Valence Compound with Single‐Step Tunneling and Multiple‐Step Hopping Behavior

et al. 2014

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The organic precursor bis(trimethylsilylethynyl)TTFMe2 (3, TTF = tetrathiafulvalene) was prepared as a 1:1 mixture of the cis and trans isomers. Pure samples of 3‐cis and 3‐trans were obtained by crystallization and identified by XRD analysis. The treatment of pure 3‐trans and a 1:1 mixture of 3‐cis/trans with (i) potassium carbonate, (ii) the iron complex Cp*(dppe)FeCl [5, Cp* = η5‐C5Me5, dppe = 1,2‐bis(diphenylphosphanyl)ethane] in the presence of KPF6, and (iii) tBuOK provided Cp*(dppe)Fe–C≡C–TTFMe2–C≡C–Fe(dppe)Cp* as the pure geometric isomer 6‐trans (85 %) and as the 60:40 mixture 6‐cis/trans (63 %), respectively. The oxidation of 6‐trans with [(C5H5)2Fe]PF6 gave [6‐trans][PF6]n (n = 1–3). Visible, IR, near‐IR (NIR), and electron paramagnetic resonance (EPR) spectroscopy together with DFT data show that [6‐trans][PF6] is a class II mixed‐valence complex (Hab = 85 cm–1) in which the spin distribution depends on the conformation of the molecule. Intramolecular electron transfer occurs through single‐step tunneling and a multistep hoping mechanism. The triplet state is thermally accessible for [6‐trans][PF6]2.

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“…This variable electronic character, together with the approximately cylindrical distribution of π electron density along the CϵC axis, has also sparked immense interest in the electronic character (mixed valence or otherwise) of radicals derived from bimetallic complexes with alkynyl-bridging ligands. [34] Transition-metal σ-alkynyl complexes have also found application as building blocks for the assembly of larger molecular structures and polymetallic complexes, and as functional materials with redox-switchable magnetic, [35] optical and non-linear optical response. [36,37] In this contribution we survey the nature of the redox processes associated with metal σ-alkynyl complexes and selected closely related systems, with particular emphasis on the chemical consequences of the change in molecular redox state.…”

Section: Introductionmentioning

confidence: 99%

Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes

Schauer

Low

2011

Eur J Inorg Chem

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Transition-metal σ-alkynyl complexes are valuable functional materials that have found application as sructural units in the assembly of polymetallic arrays and large molecular structures, reagents for the transfer, oligomerisation or functionalisation of alkynes, magnetic or optical materials and putative components for use in a future molecular-based electronics platform. Many σ-alkynyl complexes are redoxactive, undergoing facile oxidation (reduction) at moderate potentials to generate radical cations (anions) in which the

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Magnetic perturbation of the redox potentials of localized and delocalized mixed-valence complexes

Cited by 98 publications

References 65 publications

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

Synthesis and Properties of a Mixed‐Valence Compound with Single‐Step Tunneling and Multiple‐Step Hopping Behavior

Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes

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