Geometriebedingter Aromatizitätsverlust bei überbrückten [14]Annulenen:syn-1,6-Ethano-8,13-methano[14]annulen

Vogel, Emanuel; Deger, Hans M.; Hebel, Peter; Lex, Johann

doi:10.1002/ange.19800921120

Cited by 15 publications

(5 citation statements)

References 23 publications

(1 reference statement)

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“…While ab initio predictions of macromolecular interactions are still challenging, 28 DFT investigations have been shown to be particularly well suited for studying molecular and electronic structure despite placing the molecules in a markedly different environment (e.g., absolute zero and vacuum). 23,29,30 The highest occupied molecular orbital (HOMO) energy levels of the neutral oligomers in this work showed good agreement with the experimentally observed oxidation potentials, as seen in Figure 8. The ordering of polymer oxidation potentials and the relative energy difference between the oxidations are successfully reproduced for both short and long oligomers.…”

Section: Quantitative Analysis Of Charge Transfer Kinetics For the Di...supporting

confidence: 86%

“…Analysis of the oligomers indicated that all were close to being planar. Although previous experimental work has shown that conjugation is maintained until the angle between adjacent orbitals becomes large (>36°), there is a correlation between decreasing dihedral angle and increasing experimentally observed oxidation potential. Relaxed potential energy scans about the central dihedral angle of the Th derivatives indicated that less energy was required for small rotations in PDMTh than in PProDOT or PEDOT but that all of the derivatives were able to rotate up to 30° from their respective minima without significant energy cost (<1 kcal/mol).…”

Section: Resultsmentioning

confidence: 63%

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Electrochemical and Computational Studies on the Electrocatalytic Effect of Conducting Polymers toward the Redox Reactions of Thiadiazole-Based Thiolate Compounds

et al. 2010

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We have studied the electrocatalytic effects of polythiophene-based conducting polymers toward the redox reactions of the dilithium salt of the thiadiazole-based dithiol compound 2,5-dimercapto-1,3,4-thiodiazole (DMcT-2Li) via cyclic voltammetry (CV), rotating-disk electrode voltammetry, and electrochemical impedance spectroscopy (EIS). We have found that the electrocatalytic activity of the conducting polymers is strongly influenced by the potential range over which the polymers are electrically conductive (i.e., window of conductivity), which was tuned by employing different electron-donating groups at the 3-or 3,4-positions of polythiophene (PTh). Both poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT), whose windows of conductivity exhibited a good overlap with the formal potential for the dimerization process of DMcT-2Li; E 0 ′ d (-0.54 V versus Ag/Ag + ) exhibited electrocatalytic activity toward both the oxidation and reduction processes of DMcT-2Li. On the other hand, PTh, poly(3-methylthiophene) (PMTh), and poly(3,4-dimethoxythiophene) (PDMTh), whose windows of conductivity did not overlap with E 0 ′ d , did not exhibit electrocatalytic activity. The standard charge transfer rate constants for the dimerization process of DMcT-2Li at PEDOT, PProDOT, and PDMTh film-modified glassy carbon electrodes (GCEs) were estimated to be 7.4 × 10 -4 , 3.2 × 10 -4 , and 6.9 × 10 -5 cm/s while the rate constant was 6.3 × 10 -5 cm/s at an unmodified GCE. Moreover, EIS studies for PEDOT, PProDOT, and PDMTh film-modified GCEs indicated the smallest charge transfer resistance for a PEDOT film and highest for a PDMTh film at E 0 ′ d , indicating that the higher the electrical conductivity of a film at E 0 ′ d the higher the electrocatalytic activity toward the redox reactions of DMcT-2Li. These results clearly indicate that in order to accelerate the redox reactions of DMcT-2Li (and likely of other organosulfur compounds) the window of conductivity of a conducting polymer needs to overlap the formal potentials of the organosulfur compounds and, thus, support our previous observations that the electrocatalytic reactions proceed via electron exchange reactions between DMcT-2Li and conducting polymers such as PEDOT. Additional computational results for oligomers of PEDOT, ProDOT, and PDMTh showed that substituents at the 3,4-positions of the thiophene ring influence the window of conductivity via steric and electronic effects. This study provides important insights toward rational design of novel conducting-polymer-based electrocatalysts to enable organosulfur compounds to be of practical use as cathode materials for lithium-ion rechargeable batteries.

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Section: Quantitative Analysis Of Charge Transfer Kinetics For the Di...supporting

confidence: 86%

Section: Resultsmentioning

confidence: 63%

Electrochemical and Computational Studies on the Electrocatalytic Effect of Conducting Polymers toward the Redox Reactions of Thiadiazole-Based Thiolate Compounds

et al. 2010

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“…45-55Њ". 102 In keeping with this, the NMR and UV spectra of the syn-isomer 61 show it to be unequivocally an arene with a delocalised periphery, 103 whereas the anti-isomer 62 is a puckered polyalkene with fluxional π-bonds. 104 The syn-isomer forms stable orange crystals but the anti-form is sensitive to oxygen.…”

Section: Bridged [14]annulenesmentioning

confidence: 75%

Annulenes, 1980–2000

Kennedy

Lloyd

McNab

2002

J. Chem. Soc., Perkin Trans. 1

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“…Our synthetic strategy for 4 is based on 14π‐electrocyclization4, 5 across the two pentafulvenoid moieties of the precursor 6‐dimethylamino‐1‐{2‐(pentafulven‐6‐yl)ethenyl}pentafulvene ( 8 ), with formation of the central eight‐membered ring, and subsequent deamination (Scheme ). This approach is analogous to the azulene synthesis developed by Hafner and Ziegler 6…”

Section: Methodsmentioning

confidence: 99%

Dicyclopenta[a,d]cyclooctene: A [14]Annulene Containing Two Zero-Atom Cross-Links

Oda¹,

Sakamoto²,

Kajioka³

et al. 2001

Angew. Chem. Int. Ed.

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Geometriebedingter Aromatizitätsverlust bei überbrückten [14]Annulenen:syn-1,6-Ethano-8,13-methano[14]annulen

Cited by 15 publications

References 23 publications

Electrochemical and Computational Studies on the Electrocatalytic Effect of Conducting Polymers toward the Redox Reactions of Thiadiazole-Based Thiolate Compounds

Electrochemical and Computational Studies on the Electrocatalytic Effect of Conducting Polymers toward the Redox Reactions of Thiadiazole-Based Thiolate Compounds

Annulenes, 1980–2000

Dicyclopenta[a,d]cyclooctene: A [14]Annulene Containing Two Zero-Atom Cross-Links

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