Issue 71, 2024

Chemical reduction of π-expanded functionalized pentacene: cooperation of side group in alkali metal binding

Abstract

Chemical reduction of a vertically expanded pentacene, TIPS-peri-pentacenopentacene (TIPS-PPP), with sodium metal in THF readily afforded a doubly-reduced product isolated as [{Na+(THF)3}2(TIPS-PPP2−)]. Single-crystal X-ray diffraction revealed the formation of a π-complex of TIPS-PPP2− with two {Na+(THF)3} moieties. The sodium ion is coordinated to three C-atoms at the most negatively charged edge sites and at the lateral ethynyl group. The delocalisation of the charge on the ethynyl function is accompanied by its notable elongation (Δ = 0.015 Å) coupled with the contraction of the adjacent single C–C bond (Δ = 0.033 Å). Bond length analysis supported by Harmonic Aromaticity Oscillator Model (HOMA) shows that the dianion can be written with four aromatic sextets in agreement with the Clar representation. Although TIPS-PPP2− has 36 π-electrons (4n), it does not show a global magnetic paratropic response. The rings with the most negative charge density have a very low paratropic response, while the other rings have a low diatropic response. Overall, the dianion is a non-aromatic molecule.

Graphical abstract: Chemical reduction of π-expanded functionalized pentacene: cooperation of side group in alkali metal binding

Supplementary files

Article information

Article type
Communication
Submitted
03 7月 2024
Accepted
07 8月 2024
First published
14 8月 2024

Chem. Commun., 2024,60, 9526-9529

Chemical reduction of π-expanded functionalized pentacene: cooperation of side group in alkali metal binding

M. Pennachio, Z. Wei, M. Mamada, M. Frigoli and M. A. Petrukhina, Chem. Commun., 2024, 60, 9526 DOI: 10.1039/D4CC03318C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements