Putting pressure on aromaticity along with in situ experimental electron density of a molecular crystal

Nicola Casati, Annette Kleppe, Andrew P. Jephcoat, Piero Macchi

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

When pressure is applied, the molecules inside a crystal undergo significant changes of their stereoelectronic properties. The most interesting are those enhancing the reactivity of systems that would be otherwise rather inert at ambient conditions. Before a reaction can occur, however, a molecule must be activated, which means destabilized. In aromatic compounds, molecular stability originates from the resonance between two electronic configurations. Here we show how the resonance energy can be decreased in molecular crystals on application of pressure. The focus is on syn-1,6:8,13-Biscarbonyl[14]annulene, an aromatic compound at ambient conditions that gradually localizes one of the resonant configurations on compression. This phenomenon is evident from the molecular geometries measured at several pressures and from the experimentally determined electron density distribution at 7.7 GPa; the observations presented in this work are validated by periodic DFT calculations.

Original languageEnglish
Article number10901
JournalNature Communications
Volume7
DOIs
Publication statusPublished - Mar 16 2016

Fingerprint

Molecular crystals
Carrier concentration
aromatic compounds
Aromatic compounds
Electrons
Pressure
crystals
Electronic density of states
Molecules
configurations
Discrete Fourier transforms
density distribution
molecules
reactivity
Crystals
Geometry
geometry
electronics
energy

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

Cite this

Putting pressure on aromaticity along with in situ experimental electron density of a molecular crystal. / Casati, Nicola; Kleppe, Annette; Jephcoat, Andrew P.; Macchi, Piero.

In: Nature Communications, Vol. 7, 10901, 16.03.2016.

Research output: Contribution to journalArticle

Casati, Nicola ; Kleppe, Annette ; Jephcoat, Andrew P. ; Macchi, Piero. / Putting pressure on aromaticity along with in situ experimental electron density of a molecular crystal. In: Nature Communications. 2016 ; Vol. 7.
@article{4b9675b33af54d878620d1f1a28247ef,
title = "Putting pressure on aromaticity along with in situ experimental electron density of a molecular crystal",
abstract = "When pressure is applied, the molecules inside a crystal undergo significant changes of their stereoelectronic properties. The most interesting are those enhancing the reactivity of systems that would be otherwise rather inert at ambient conditions. Before a reaction can occur, however, a molecule must be activated, which means destabilized. In aromatic compounds, molecular stability originates from the resonance between two electronic configurations. Here we show how the resonance energy can be decreased in molecular crystals on application of pressure. The focus is on syn-1,6:8,13-Biscarbonyl[14]annulene, an aromatic compound at ambient conditions that gradually localizes one of the resonant configurations on compression. This phenomenon is evident from the molecular geometries measured at several pressures and from the experimentally determined electron density distribution at 7.7 GPa; the observations presented in this work are validated by periodic DFT calculations.",
author = "Nicola Casati and Annette Kleppe and Jephcoat, {Andrew P.} and Piero Macchi",
year = "2016",
month = "3",
day = "16",
doi = "10.1038/ncomms10901",
language = "English",
volume = "7",
journal = "Nature Communications",
issn = "2041-1723",
publisher = "Nature Publishing Group",

}

TY - JOUR

T1 - Putting pressure on aromaticity along with in situ experimental electron density of a molecular crystal

AU - Casati, Nicola

AU - Kleppe, Annette

AU - Jephcoat, Andrew P.

AU - Macchi, Piero

PY - 2016/3/16

Y1 - 2016/3/16

N2 - When pressure is applied, the molecules inside a crystal undergo significant changes of their stereoelectronic properties. The most interesting are those enhancing the reactivity of systems that would be otherwise rather inert at ambient conditions. Before a reaction can occur, however, a molecule must be activated, which means destabilized. In aromatic compounds, molecular stability originates from the resonance between two electronic configurations. Here we show how the resonance energy can be decreased in molecular crystals on application of pressure. The focus is on syn-1,6:8,13-Biscarbonyl[14]annulene, an aromatic compound at ambient conditions that gradually localizes one of the resonant configurations on compression. This phenomenon is evident from the molecular geometries measured at several pressures and from the experimentally determined electron density distribution at 7.7 GPa; the observations presented in this work are validated by periodic DFT calculations.

AB - When pressure is applied, the molecules inside a crystal undergo significant changes of their stereoelectronic properties. The most interesting are those enhancing the reactivity of systems that would be otherwise rather inert at ambient conditions. Before a reaction can occur, however, a molecule must be activated, which means destabilized. In aromatic compounds, molecular stability originates from the resonance between two electronic configurations. Here we show how the resonance energy can be decreased in molecular crystals on application of pressure. The focus is on syn-1,6:8,13-Biscarbonyl[14]annulene, an aromatic compound at ambient conditions that gradually localizes one of the resonant configurations on compression. This phenomenon is evident from the molecular geometries measured at several pressures and from the experimentally determined electron density distribution at 7.7 GPa; the observations presented in this work are validated by periodic DFT calculations.

UR - http://www.scopus.com/inward/record.url?scp=84982153298&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84982153298&partnerID=8YFLogxK

U2 - 10.1038/ncomms10901

DO - 10.1038/ncomms10901

M3 - Article

VL - 7

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

M1 - 10901

ER -