Electron spin resonance study of a spirotetraene and a spirodienone radical anion

Gerson, Fabian; Gleiter, Rolf; Moshuk, G.; Dreiding, Aǹdré S.

doi:10.1021/ja00764a003

Cited by 27 publications

(5 citation statements)

References 4 publications

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“…Angewandte Chemie Spirodienonen [47] (z. B. O), Hexa-tert-butyldiphenylacetylen [48] P und cis-10,11-Dimethyldiphensuccindan-9,12-dion [49] Q, dass die Ladung innerhalb der ESR-Zeitskala in z.…”

Section: Gemischtvalente Verbindungenunclassified

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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Section: Gemischtvalente Verbindungenunclassified

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

2011

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“…Furthermore, ESR investigations on the spin-density distribution of the radical anions of paracyclophane derivatives [43][44][45] (e.g. M), phenylcyclooctatetraene [46] N, spirodienones [47] (e.g. O), hexa-tert-butyldiphenylacetylene [48] P, and cis-10,11-dimethyldiphensuccindan-9,12-dione [49] Q showed the charge to be localized, for example, in L, O, and Q and delocalized in, for example, M and P on the ESR time scale.…”

Section: Introductionmentioning

confidence: 99%

Organic Mixed‐Valence Compounds: A Playground for Electrons and Holes

Heckmann¹,

Lambert²

2011

Angew Chem Int Ed

509

495

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Mixed-valence (MV) compounds are excellent model systems for the investigation of basic electron-transfer (ET) or charge-transfer (CT) phenomena. These issues are important in complex biophysical processes such as photosynthesis as well as in artificial electronic devices that are based on organic conjugated materials. Organic MV compounds are effective hole-transporting materials in organic light emitting diodes (OLEDs), solar cells, and photochromic windows. However, the importance of organic mixed-valence chemistry should not be seen in terms of the direct applicability of these species but the wealth of knowledge about ET phenomena that has been gained through their study. The great variety of organic redox centers and spacer moieties that may be combined in MV systems as well as the ongoing refinement of ET theories and methods of investigation prompted enormous interest in organic MV compounds in the last decades and show the huge potential of this class of compounds. The goal of this Review is to give an overview of the last decade in organic mixed valence chemistry and to elucidate its impact on modern functional materials chemistry.

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“…The spiro center linking two Ni(II) corroles renders this cyclooctapyrrole unique and poses the question of how the spiro carbon influences electronic interaction between the two halves. With the aim of better understanding this system and to establish the existence of spiro conjugation in compound 1b , we set out to prepare an appropriate reference compound. Cyclotetrapyrrole 2a (Figure ), in which the geminal ( gem ) dimethyl carbon replaces the spiro carbon of 1a , b , represents an appropriate reference with respect to complex 1b .…”

Section: Introductionmentioning

confidence: 99%

Competitive Formation of Helical Cycloocta- and Cyclododecapyrroles

et al. 2000

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In connection with a study aimed at the evaluation of electronic effects in spiro-dicorrole (1a) and its binuclear Ni(II) complex (1b) we became interested in gem-dimethyl-substituted cyclotetrapyrrole (2a) and the corresponding Ni(II) complex (2b). Attempts to prepare 2a as the 12,13,16,17-tetraethyl-2,3,7, 8-tetramethyl derivative (5) by an acid-catalyzed (1 + 1) condensation of dimethyldipyrrylmethane 3 and diformylbipyrrole 4 resulted in the formation of the (2 + 2) and (3 + 3) condensation products, i.e., the cyclooctapyrrole 6 and the cyclododecapyrrole 7, respectively, rather than in that of the desired gem-dimethyl cyclotetrapyrrole. The cyclododecapyrrole 7, isolated as the major product, is among the largest cyclopolypyrroles known to date. These two new macrocycles have been structurally characterized by variable temperature 1D and 2D NMR experiments, as well as by single-crystal X-ray diffraction analysis. In solution both the cyclooctapyrrole 6 and cyclododecapyrrole 7 exhibit dynamic behavior. At 337 K 6 adopts a D(2)-symmetric conformation, whereas at 196 K two equivalent C(2) conformers that interconvert through the D(2)-symmetric intermediate are observed. The energy barrier for the interconversion process between these two degenerate conformers is found to be 10.6 kcal mol(-)(1). The solution dynamics of 7 could be described in an analogous manner, with the time-averaged conformation at 378 K displaying D(3)(h)() symmetry. X-ray analyses showed that for both macrocycles, 6 and 7, the solid state structures were nearly identical to the low-temperature solution conformers.

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Electron spin resonance study of a spirotetraene and a spirodienone radical anion

Cited by 27 publications

References 4 publications

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

Organische gemischtvalente Verbindungen: ein Spielplatz für Elektronen und Löcher

Organic Mixed‐Valence Compounds: A Playground for Electrons and Holes

Competitive Formation of Helical Cycloocta- and Cyclododecapyrroles

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