Preparation and Structures of Crystalline Aromatic Cation-Radical Salts. Triethyloxonium Hexachloroantimonate as a Novel (One-Electron) Oxidant

Rathore, Rajendra; Kumar, Anil; Lindeman, Sergey V.; Kochi, Jay K.

doi:10.1021/jo980407a

Cited by 136 publications

(128 citation statements)

References 57 publications

(53 reference statements)

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“…30c The neutral precursors of tris(2,4-dibromobenzene)amine, tris(4-bromobenzene)amine, and their radical cations (MG •+ ) as hexachloroantimonate and hexafluorophosphate salts were prepared according to the literature procedure. 54 All of the compounds prepared were characterized by 1 H NMR, 13 C NMR, MS, melting points, and elemental analysis. The methylene-bridged alkyhydroquinones were readily prepared in two steps.…”

Section: Discussionmentioning

confidence: 99%

“…The purities of all salts were determined by iodometric titration and were found to be greater than 98%. 13 The dication 3 2+ and cation radicals and dications of donors 7−10 were not isolated in the solid state, owing to partial decomposition in the process of oxidation/isolation; they were therefore prepared and examined in situ, as described below.…”

Section: Isolation Of Mixed-valence Cation-radical and Dicationmentioning

confidence: 99%

“…For quantitative studies of the energetics, structures, and optical transitions in such dimer cation-radical assemblies, we focus on Ar = 2,5-dimethoxy-p-tolyl (T), owing to the reversible oxidation of this aromatic group to generate its persistent cation radical (T •+ ) at an accessible potential of E°ox = 1.10 V vs SCE. [13][14][15] Chart 2…”

Section: Chartmentioning

confidence: 99%

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Intervalence (Charge-Resonance) Transitions in Organic Mixed-Valence Systems. Through-Space versus Through-Bond Electron Transfer between Bridged Aromatic (Redox) Centers

et al. 2003

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Intervalence absorption bands appearing in the diagnostic near-IR region are consistently observed in the electronic spectra of mixed-valence systems containing a pair of aromatic redox centers (Ar •+ /Ar) that are connected by two basically different types of molecular bridges. The through-space pathway for intramolecular electron transfer is dictated by an o-xylylene bridge in the mixed-valence cation radical 3•+ with Ar = 2,5-dimethoxy-p-tolyl (T), in which conformational mobility allows the proximal syn disposition of planar T•+ /T redox centers. Four independent experimental probes indicate the large through-space electronic interaction between such cofacial Ar•+ /Ar redox centers from the measurements of (a) sizable potential splitting in the cyclic voltammogram, (b) quinonoidal distortion of T•+ /T centers by X-ray crystallography, (c) "doubling" of the ESR hyperfine splittings, and (d) a pronounced intervalence charge-resonance band. The through (br)-bond pathway for intramolecular electron transfer is enforced in the mixed-valence cation radical 2a•+ by the p-phenylene bridge which provides the structurally inflexible and linear connection between Ar•+ /Ar redox centers. The direct comparison of intramolecular rates of electron transfer (kET) between identical T•+ /T centers in 3•+ and 2a•+ indicates that through-space and through-bond mechanisms are equally effective, despite widely different separations between their redox centers. The same picture obtains for 3•+ and 2a•+ from theoretical computations of the first-order rate constants for intramolecular electron transfer from Marcus−Hush theory using the electronic coupling elements evaluated from the diagnostic intervalence (charge-transfer) transitions. Such a strong coherence between theory and experiment also applies to the mixed-valence cation radical 7•+ , in which the aromatic redox S center is sterically encumbered by annulation.

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Section: Discussionmentioning

confidence: 99%

Section: Isolation Of Mixed-valence Cation-radical and Dicationmentioning

confidence: 99%

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Intervalence (Charge-Resonance) Transitions in Organic Mixed-Valence Systems. Through-Space versus Through-Bond Electron Transfer between Bridged Aromatic (Redox) Centers

et al. 2003

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“…[192,236,237] [a] Die Radikalkationen wurden durch chemische Oxidation mit OMNSbCl 6 [238] in Dichlormethan erzeugt. [192] (OMN = 2,3,8,9-Tetrahydro-1,1,4,4,7,7,10,10-octamethyltetracen).…”

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Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

2011

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Gemischtvalente (MV) Verbindungen sind ausgezeichnete Modellsysteme, um grundlegende Elektronentransport(ET)‐ und Ladungstransfer(CT)‐Phänomene zu untersuchen. Diese sind in komplexen biophysikalischen Prozessen wie der Photosynthese, aber auch in artifiziellen elektronischen Bauteilen von großer Bedeutung. So sind organische MV‐Verbindungen effiziente Lochtransportmaterialien in organischen lichtemittierenden Dioden (OLEDs), Solarzellen und photochromen Fenstern. Die Bedeutung der organischen gemischtvalenten Chemie sollte jedoch weniger in ihrer direkten Anwendbarkeit gesehen werden, als vielmehr in dem riesigen Kenntnisschatz über Elektronentransferphänomene, der durch ihr Studium gewonnen wurde. Die große Vielfalt an organischen Redoxzentren und Brückeneinheiten, die zu MV‐Verbindungen kombiniert werden können, sowie die stete Weiterentwicklung von ET‐Theorien und ET‐Untersuchungsmethoden förderten das enorme Interesse an organischen MV‐Verbindungen in den letzten Jahrzehnten und zeigen das große Potential dieser Verbindungsklasse auf. Das Ziel dieses Aufsatzes ist es, das letzte Jahrzehnt der organischen gemischtvalenten Chemie zusammenzufassen und ihren Einfluss auf moderne funktionelle Materialien hervorzuheben.

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“…However, since has been reported that SbCl 5 reacts through the formation of cation-radical intermediates in similar reaction conditions, 14 a radical mechanism hypothesis could not definitively be excluded. Further investigations are actually in progress on this point, aimed also to a full characterization of the reaction intermediates 3a-c by X-ray crystallography.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of N,N,N’,N’-tetraalkylbenzidines through oxidative coupling of N,N-dialkylarylamines induced by SbCl5

Vitale¹,

Nunno²,

Scilimati³

2013

Arkivoc

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Preparation and Structures of Crystalline Aromatic Cation-Radical Salts. Triethyloxonium Hexachloroantimonate as a Novel (One-Electron) Oxidant

Cited by 136 publications

References 57 publications

Intervalence (Charge-Resonance) Transitions in Organic Mixed-Valence Systems. Through-Space versus Through-Bond Electron Transfer between Bridged Aromatic (Redox) Centers

Intervalence (Charge-Resonance) Transitions in Organic Mixed-Valence Systems. Through-Space versus Through-Bond Electron Transfer between Bridged Aromatic (Redox) Centers

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

Synthesis of N,N,N’,N’-tetraalkylbenzidines through oxidative coupling of N,N-dialkylarylamines induced by SbCl5

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