Issue 19, 2012

Controlling the local arrangements of π-stacked polycyclic aromatic hydrocarbons through substituent effects

Abstract

PAHs such as coronene and hexa-peri-hexabenzocoronene (HBC, a nanographene) are commonly used in discotic liquid crystals, for which achieving long-range columnular order is vital for the development of materials with maximized charge-transfer rates. We demonstrate that simple substituents can have a dramatic impact on the local orientation of π-stacked polycyclic aromatic hydrocarbons (PAHs), even in the absence of steric or other non-covalent interactions (e.g.: hydrogen bonds). The strong dependence of these π-stacking interactions on the relative position of substituents is a result of the direct, through-space interactions of aryl substituents. B97-D/TZV(2d,2p) interaction energies are presented for stacked dimers of substituted benzenes, coronenes, and HBC, which display diverse orientation potentials depending on the nature of the substituents. The results show that the position of the global energy minimum for stacked PAHs depends on the nature of the aryl substituents. The preferred arrangement of stacked coronenes, for example, can be shifted from a fully staggered arrangement to a fully eclipsed arrangement through the introduction of complementary pairs of substituents.

Graphical abstract: Controlling the local arrangements of π-stacked polycyclic aromatic hydrocarbons through substituent effects

Supplementary files

Article information

Article type
Paper
Submitted
24 Apr 2012
Accepted
18 May 2012
First published
23 May 2012

CrystEngComm, 2012,14, 6140-6145

Controlling the local arrangements of π-stacked polycyclic aromatic hydrocarbons through substituent effects

S. E. Wheeler, CrystEngComm, 2012, 14, 6140 DOI: 10.1039/C2CE25630D

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