X-ray Structural Characterization of Charge Delocalization onto the Three Equivalent Benzenoid Rings in Hexamethoxytriptycene Cation Radical

Chebny, Vincent J.; Navale, Tushar S.; Shukla, Ruchi; Lindeman, Sergey V.; Rathore, Rajendra

doi:10.1021/ol900558s

Cited by 26 publications

(35 citation statements)

References 34 publications

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“…5). Indeed, the experimental MF/D points fall exactly on the predicted lines, obtained using the electrochemical redox potential E ox1 (DMB) = 0.82 V, [19] confirming that the relative first oxidation potentials of THEO and DMB are not impacted by the presence/absence of electrolyte.…”

Section: +supporting

confidence: 76%

Quantitative generation of cation radicals and dications using aromatic oxidants: effect of added electrolyte on the redox potentials of aromatic electron donors

Talipov

Boddeda

Hossain

et al. 2015

J of Physical Organic Chem

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Redox titrations using robust aromatic oxidants allow for a quantitative analysis of redox and optical properties of organic electron donors in their oxidized states. Unlike spectroelectrochemistry, redox titrations can be performed without added electrolyte in relatively nonpolar solvents, affording quick access to the redox and optical properties of a given electron donor without the need of a complex electrochemical setup. However, the redox potentials obtained by the two methods are not the same. To establish the direction and magnitude of this discrepancy, we have performed a systematic case study using a set of tetraarylethylene donors and a tetrasubstituted hydroquinone ether cation radical () as a stable aromatic oxidant. We show that redox potentials (especially second and higher oxidation potentials) measured by electrochemical methods are systematically lower compared with the redox potentials obtained by redox titrations in the absence of electrolyte, because of the enhanced stabilization of dications and polycations by electrolyte. We have also uncovered that the smaller cation radicals (e.g., a para-hydroquinone or ortho-hydroquinone ether cation radicals) are much more effectively stabilized when compared with the cation radicals in which charge is delocalized over larger area (e.g., tetraarylethylene cation radicals) in the presence of electrolyte because of increased ionic strength of the solution.

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Section: +supporting

confidence: 76%

Quantitative generation of cation radicals and dications using aromatic oxidants: effect of added electrolyte on the redox potentials of aromatic electron donors

Talipov

Boddeda

Hossain

et al. 2015

J of Physical Organic Chem

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“…The simplest example of apical [23] aromatic homoconjugated compound should be diphenylmethane (DPM, 16; Figure 2). [24] However, aryl-aryl interactions in diaryl-A C H T U N G T R E N N U N G methanes are governed by repulsive electrostatic forces [25] and, therefore, the most stable conformation of 16 is the helical disposition, in which the homoconjugative interaction between the phenyl rings is not possible.…”

Section: Resultsmentioning

confidence: 99%

Electron Delocalization in Homoconjugated 7,7‐Diarylnorbornane Systems: A Computational and Experimental Study

Herrero-García

Fernández

Barcina

2011

Chemistry A European J

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A joint computational-experimental study has been carried out to analyze the homoconjugative interactions in 7,7-diarylnorbornane (DPN) derivatives. The experimentally observed new bands in their UV/Vis have been accurately assigned by means of TD-DFT calculations. Both experimental data and computations show that aromatic homoconjugation in acyclic systems is an effective mechanism for electron delocalization that resembles the situation described for polyphenylenes and polyenes. The effective homoconjugation length in homoconjugated oligomers is in the range of 6-7 aryl rings. The effect of substituents directly attached to the para carbon atom of the DPN moiety have been also studied. We found that the HOMO→LUMO vertical transitions can indeed be modified by the nature of the aromatic substituents in order to provoke dramatic changes in the electronic properties (i.e., in the absorption spectra) of the studied species.

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“…Their unique molecular configuration have found application in various functional areas, for instance, as molecular motors and as ligands . Furthermore, chemical modification such as π‐fusion or substituent introduction on triptycene or trinaphtho[3.3.3]propellane (TNP, 1 , Scheme ), induces a strong π‐π interaction between molecules, leading to two‐dimensional (2D) molecular assemblies . In addition to their geometrical uniqueness, homoconjugation among three arenes have been active subjects of investigation due to the importance for both fundamental science and application in organic semiconductors such as OFET and photovoltaics.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Electronic Properties of Triperyleno[3.3.3]Propellanes: Towards Two‐Dimensional Electronic Structures

2019

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Threefold symmetric triperyleno[3.3.3]propellanes (TPRPs), which are composed of three perylene units peri‐fused on [3.3.3]proppellane, have been synthesized and their electronic properties characterized. Unsubstituted TPRP assembles into two‐dimensional honeycomb‐like networks. TPRP displays a bathochromic‐shifted absorption band in its absorption spectrum and shows well‐separated one‐electron redox waves in a cyclic voltammogram, due to a homoconjugative interaction between perylene moieties. A radical cation species of tert‐butyl substituted TPRP shows spin delocalization over the whole of the molecule, which is derived from effective overlap of HOMOs among three perylene moieties.

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X-ray Structural Characterization of Charge Delocalization onto the Three Equivalent Benzenoid Rings in Hexamethoxytriptycene Cation Radical

Abstract: This paper is NOT THE PUBLISHED VERSION; but the author's final, peer-reviewed manuscript. The published version may be accessed by following the link in th citation below.

Cited by 26 publications

References 34 publications

Quantitative generation of cation radicals and dications using aromatic oxidants: effect of added electrolyte on the redox potentials of aromatic electron donors

Quantitative generation of cation radicals and dications using aromatic oxidants: effect of added electrolyte on the redox potentials of aromatic electron donors

Electron Delocalization in Homoconjugated 7,7‐Diarylnorbornane Systems: A Computational and Experimental Study

Synthesis and Electronic Properties of Triperyleno[3.3.3]Propellanes: Towards Two‐Dimensional Electronic Structures

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