From corannulene to indacenopicene: Effect of carbon framework topology on aromaticity and reduction limits

Spisak SN, Li J, Rogachev AY, Wei Z, Papaianina O, Amsharov K, Rybalchenko AV, Goryunkov AA, Petrukhina MA (2016)

Publication Type: Journal article

Publication year: 2016

Journal

Organometallics American Chemical Society

Book Volume: 35

Pages Range: 3105-3111

Journal Issue: 18

DOI: 10.1021/acs.organomet.6b00395

Abstract

The electronic structure, reduction limits, and coordination abilities of a bowl-shaped polycyclic aromatic hydrocarbon, indacenopicene (C26H12, 1), have been investigated for the first time using a combination of theoretical and experimental tools. A direct comparison with the prototypical corannulene bowl (C20H10, 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 [M2(18-crown-6)]²⁺ (M = Rb (3) and Cs (4)) cations occupying the concave cavities of two C26H12^2- 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(C26H12^2-)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)(C26H12^2-)]∞.

Authors with CRIS profile

Olena Papaianina Lehrstuhl für Organische Chemie II Konstantin Amsharov Lehrstuhl für Organische Chemie II

Involved external institutions

State University of New York at Albany (UNY Albany / UAlbany)

United States (USA) (US) Indian Institute of Technology (IIT) Gandhinagar

India (IN) Lomonosov Moscow State University / Московский государственный университет имени М.В.Ломоносова

Russian Federation (RU)

How to cite

APA:

Spisak, S.N., Li, J., Rogachev, A.Y., Wei, Z., Papaianina, O., Amsharov, K.,... Petrukhina, M.A. (2016). From corannulene to indacenopicene: Effect of carbon framework topology on aromaticity and reduction limits. Organometallics, 35(18), 3105-3111. https://doi.org/10.1021/acs.organomet.6b00395

MLA:

Spisak, Sarah N., et al. "From corannulene to indacenopicene: Effect of carbon framework topology on aromaticity and reduction limits." Organometallics 35.18 (2016): 3105-3111.

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