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Issue 14, 2021

Mutually exclusive hole and electron transfer coupling in cross stacked acenes

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Abstract

The topology of frontier molecular orbitals (FMOs) induces highly sensitive charge transfer coupling with variation in the intermolecular arrangement. A consistent optoelectronic property correlated to a specific aggregate architecture independent of the nature of the monomer is a rare phenomenon. Our theoretical investigation on stacked dimeric systems of linear [n]acenes (n = 2–5) and selected non-linear acenes with a D2h point group reveals that the Greek cross (+) stacked orientation, irrespective of the molecular candidate, exhibits mutually exclusive hole and electron transfer couplings. The deactivation of either hole or electron transfer coupling is a consequence of the zero inter-orbital overlap between the highest occupied molecular orbitals (HOMOs) or lowest unoccupied molecular orbitals (LUMOs) of the monomers possessing gerade symmetry. In the Greek cross (+) stacked alignment, the (4n + 2) π-electronic acene systems with an odd number of benzenoids exhibit exclusive electron transfer coupling, while the even numbered acenes exhibit selective hole transfer coupling. The trend is reversed for representative 4n π-electronic acene systems. The effect of mutually exclusive charge transfer coupling in the hopping regime of charge transport was evaluated using semiclassical Marcus theory, and selective charge carrier mobility was exhibited by the Greek cross (+) stacks of the considered acene candidates. Additionally, the characteristic charge transfer coupling of the orthogonal acene stacks resulted in negligible short-range exciton coupling, inciting null exciton splitting at short interplanar distances. Engineering chromophores in precise angular orientations ensuring characteristic emergent properties can have tremendous potential in the rational design of advanced optoelectronic materials.

Graphical abstract: Mutually exclusive hole and electron transfer coupling in cross stacked acenes

Supplementary files

Article information


Submitted
27 Jan 2021
Accepted
16 Mar 2021
First published
17 Mar 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 5064-5072
Article type
Edge Article

Mutually exclusive hole and electron transfer coupling in cross stacked acenes

A. Benny, R. Ramakrishnan and M. Hariharan, Chem. Sci., 2021, 12, 5064 DOI: 10.1039/D1SC00520K

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