C30H126−: Self‐Aggregation, High Charge Density, and Pyramidalization in a Supramolecular Structure of a Supercharged Hemifullerene

Treitel, Noach; Sheradsky, Tuvia; Peng, Li; Scott, Lawrence T.; Rabinovitz, Mordecai

doi:10.1002/anie.200503542

Cited by 31 publications

(9 citation statements)

References 84 publications

(21 reference statements)

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“…The 13 C− 1 H coupling supports this observation, with J C−H for the 2−4 positions on the anthracene core in the range of 157− 163 Hz for all Ant-Cn, indicating no pyramidalization in these carbons (Table S2, see SI). 24 Acenes have a typical UV−vis absorption spectrum composed mainly of β and p ( 1 L a state) bands. 25 Upon twisting, an increase in the intensity of the p band is clearly observed.…”

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confidence: 99%

Helically Locked Tethered Twistacenes

2018

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Twisting linear acenes out of planarity affects their electronic and optical properties, and induces chirality. However, it is difficult to isolate the effect of twisting from the substituent effect. Moreover, many twistacenes (twisted acenes) readily racemize in solution. Here, we introduce a series of twistacenes having an anthracene backbone diagonally tethered by an n-alkyl bridge, which induces a twist of various angles. This allows us to systematically monitor the effect of twisting on electronic and optical properties. We find that absorption is bathochromically shifted with increasing twist, while fluorescence quantum efficiency drops dramatically. The tethered twistacenes were isolated to their enantiomerically pure form, displaying strong chiroptical properties and anisotropy factor ( g-value). No racemization was observed even upon prolonged heating, rendering these tethered twistacenes suitable as enantiopure helical building units for π-conjugated backbones.

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confidence: 99%

Helically Locked Tethered Twistacenes

2018

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“… At the same time, theoretical studies of large and deep π-bowls confirm their great potential for selective endohedral metal encapsulation . Furthermore, NMR investigations of alkali-metal-induced reduction of C 26 H 12 , C 28 H 14 , and C 30 H 12 predicted the formation of unique supramolecular assemblies in solution, showing that the ligating properties of neutral π-bowls can be enhanced by stepwise addition of electrons. However, none of the above-mentioned products have been isolated in the solid state and crystallographically characterized.…”

Section: Introductionmentioning

confidence: 87%

From Corannulene to Indacenopicene: Effect of Carbon Framework Topology on Aromaticity and Reduction Limits

Spisak

Rogachev

et al. 2016

Organometallics

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The electronic structure, reduction limits, and coordination abilities of a bowl-shaped polycyclic aromatic hydrocarbon, indacenopicene (C 26 H 12 , 1), have been investigated for the first time using a combination of theoretical and experimental tools. A direct comparison with the prototypical corannulene bowl (C 20 H 10 , 2) revealed the effects of carbon framework topology and symmetry change on the electronic properties and aromaticity of indacenopicene. The accessibility of two reduction steps for 1 was predicted theoretically and then confirmed experimentally. Two reversible one-electron reduction processes with the formal reduction potentials at −1.92 and −2.29 V vs Fc +/0 were detected by cyclic voltammetry measurements, demonstrating the stability of the corresponding mono-and dianionic states of 1. The products of the doubly reduced indacenopicene have been isolated as rubidium and cesium salts and fully characterized. Their X-ray diffraction study revealed the formation of tetranuclear organometallic building blocks with the [M 2 (18-crown-6)] 2+ (M = Rb (3) and Cs (4)) cations occupying the concave cavities of two C 26 H 12 2− anions. The coordination of two outside exo-bound rubidium ions is terminated by crown ether molecules in 3 to form the discrete [Rb + 4 (18-crown-6) 3 (C 26 H 12 2− ) 2 ] tetramer. In contrast, the larger cesium ions allow the 1D polymeric chain propagation in 4 to afford [Cs + 2 (18-crown-6) 2 (THF)(C 26 H 12 2−)] ∞ .

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“…Finally we investigated the electrochemical properties of 1 by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) using 0.10 m Et 4 NBF 4 as supporting electrolyte ( Figure 5). Thec yclic voltammogram of 1 in benzonitrile is remarkable,thus displaying four oxidation potentials for five electrons at À0.03, + 0.23, + 0.44, and + 0.73 (for 2e)V (versus Fc/Fc + )all as fully reversible waves,thus implying the multicharge storage ability of 1.T othe best of our knowledge, this is the largest number for electron donation from adiscrete single component all-carbon structure.C 60 and C 70 are known to accept six electrons, [19] thus 1 is anice counterpart of C 60 in terms of stable multicharge-storage nanocarbon materials. From the first oxidation potential, we could estimate the HOMO level to be À4.77 eV,which is in accord with the MO calculation.…”

Section: Methodsmentioning

confidence: 99%

Tetrabenzoperipentacene: Stable Five‐Electron Donating Ability and a Discrete Triple‐Layered β‐Graphite Form in the Solid State

et al. 2015

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An oxidative ring-closure reaction of at etranaphthylpyrene derivative led to the synthesis of a5 6a ll-carbon conjugated tetrabenzoperipentacene.I nt he single-crystal Xray structure,t hree molecules make at riple-layered cluster by p-stacking,w herein each layer rotates by 1208 8,a nd is thus considered apetit b-graphite.Asfor the optical properties,the Stokes shift is extremely small (10 cm À1 ), thus indicating its remarkably rigid framework. The tetrabenzoperipentacene exhibits reversible five-electron oxidation waves in cyclic voltammetry,and is regarded as ac ounterpart to the fullerene C 60 in terms of stable multicharge-storage nanocarbon materials. Scheme 1. Resonance structures of aperipentacene.the planes in the unit are about 3.4 , just within van der Waals distances.The layered structure of 1 is the same as that for b-graphite.The rigidity of this carbon sheet was confirmed by the sharp 0-0 absorption band and the remarkably small Stokes shift (only 10 cm À1 ). We observed reversible fiveelectron oxidation waves,t hus revealing the superior redox behavior of the molecular multicharge-storage graphene.

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C₃₀H₁₂⁶⁻: Self‐Aggregation, High Charge Density, and Pyramidalization in a Supramolecular Structure of a Supercharged Hemifullerene

Cited by 31 publications

References 84 publications

Helically Locked Tethered Twistacenes

Helically Locked Tethered Twistacenes

From Corannulene to Indacenopicene: Effect of Carbon Framework Topology on Aromaticity and Reduction Limits

Tetrabenzoperipentacene: Stable Five‐Electron Donating Ability and a Discrete Triple‐Layered β‐Graphite Form in the Solid State

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