2002
DOI: 10.1039/b210429f
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An anionic organic mixed-valence system with a remarkably well-resolved vibrational structure in its intervalence band

Abstract: The reduction of a phenylene-bridged bis(dioxaborine) affords a strongly delocalised organic mixed-valence system; for the first time details of the vibrations coupled to the electron transfer have been extracted from the intervalence band.

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Cited by 28 publications
(36 citation statements)
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“…Moreover, the study of their properties should lead to the synthesis of systems in which the electron transfer could be finely tuned in a far more precise way than have been done with coordination compounds. Representative examples of the different types of electroactive organic units so far used are: i) anion radicals derived from conjugated diquinones and diimides, [7] ii) cation radicals derived from bis(tetrathiafulvalenes), [8] iii) cation radicals derived from bis(hydrazines), [9] iv) quinoid groups, [10] and v) ion radicals derived from p-conjugated polyarylmethyl/polyarylamines/polychlorotriphenylmethyl radicals [11] and bridged dinitroaromatic radical and bis(dioxaborine)anions mixed-valence systems [12] among others.…”
Section: Ma C H T U N G T R E N N U N G (Cat-n-bq)a C H T U N G T R Ementioning
confidence: 99%
“…Moreover, the study of their properties should lead to the synthesis of systems in which the electron transfer could be finely tuned in a far more precise way than have been done with coordination compounds. Representative examples of the different types of electroactive organic units so far used are: i) anion radicals derived from conjugated diquinones and diimides, [7] ii) cation radicals derived from bis(tetrathiafulvalenes), [8] iii) cation radicals derived from bis(hydrazines), [9] iv) quinoid groups, [10] and v) ion radicals derived from p-conjugated polyarylmethyl/polyarylamines/polychlorotriphenylmethyl radicals [11] and bridged dinitroaromatic radical and bis(dioxaborine)anions mixed-valence systems [12] among others.…”
Section: Ma C H T U N G T R E N N U N G (Cat-n-bq)a C H T U N G T R Ementioning
confidence: 99%
“…Außerdem konnten die Parameter der inneren (l v ) und der Lçsungs-mittelreorganisation (l o ) unabhängig durch Berechnung von l v aus den Schwingungskraftkonstanten ermittelt werden, die wiederum aus den entsprechenden Schwingungsspektren erhalten wurden. [253] Wie man an den gesammelten Daten in [255] Sowohl ZINDO-als auch DFT-Rechnungen bestätigten den Klasse-III-Charakter, was darauf schließen lässt, dass die negative Ladung symmetrisch über die Dioxaborin-Redoxzentren verteilt ist. Während DFT üblicherweise die Ladungsdelokalisierung überbewertet, ist die berechnete IV-CTBandenenergie in vernünftiger Übereinstimmung mit dem Experiment.…”
unclassified
“…Zusätzlich konnte die CT-Bande mit einem vibronischen Modell simuliert werden, bei dem nur totalsymmetrische Banden berücksichtigt wurden. [255] Die Moden, die zur Schwingungsstruktur der CT-Bande beitragen, konnten bestimmt werden, und die gesamte Marcus-Reorganisationsenergie l = 1450 cm À1 wurde berechnet. [255] Die relativ kleine Reorganisationsenergie kommt wahrscheinlich durch die sehr kleinen geometrischen Veränderungen während des Ladungstransfers zustande, was von den DFT-Rechnungen vorausgesagt wurde.…”
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“…ESR experiments reveal that DOBs can produce relatively stable radical anions through single electron transfer process. The photoexcited state of DOB molecules undergoes investigation for a wide variety of functionalities, such as photo cyclic additions, photo-induced electron transfers, and silver photo depositions [21,22] .…”
mentioning
confidence: 99%