Theoretical study of stability and charge-transport properties of coronene molecule and some of its halogenated derivatives: A path to ambipolar organic-based materials?

Abstract

We have carefully investigated the structural and electronic properties of coronene and some of its fluorinated and chlorinated derivatives, including full periphery substitution, as well as the preferred orientation of the non-covalent dimer structures subsequently formed. We have paid particular attention to a set of methodological details, to first obtain single-molecule magnitudes as accurately as possible, including next the use of modern dispersion-corrected methods to tackle the corresponding non-covalently bound dimers. Generally speaking, this class of compounds is expected to self-assembly in neighboring π -stacks with dimer stabilization energies ranging from -20 to -30 kcal mol −1 at close distances around 3.0-3.3 Å. Then, in a further step, we have also calculated hole and electron transfer rates of some suitable candidates for ambipolar materials, and corresponding charge mobility values, which are known to critically depend on the supramolecular organization of the samples. For coronene and per-fluorinated coronene, we have found high values for their hopping rates, although slightly smaller for the latter due to an increase (decrease) of the reorganization energies (electronic couplings).

Theoretical study on the electron transport properties of chlorinated pentacene derivatives

“…As seen, the studied molecules possess large vertical EA (EA v , 1.80-2.69 eV) and vertical IP (IP v , 6.37-6.88 eV) values, which correspond to their low LUMO and HOMO levels. Note that the same findings have been previously found for chlorinated chrysene and coronene derivatives [12,13]. Their large EA(v) value give rise to high stability of their anions in ambient atmosphere, which is an important requirement for good n-type OFET materials.…”

“…Also Bao et al [11] have considered that chlorinated molecules behave as well or better than their fluorinated compounds in terms of electron mobility and ambient stability. Recently, chlorinated chrysene [12] and coronene derivatives [13] have been investigated which are all shown larger EAs to facilitate the electron injection from the metallic electrode. As compared to polycyclic aromatic hydrocarbons (PAHs) and heteroacenes, chlorinated linear acenes are rarely studied systematically.…”

Dependence upon charge of the vibrational spectra of small Polycyclic Aromatic Hydrocarbon clusters: the example of pyrene

“…For instance, their role in flame chemistry is still under debate, as they could act as possible precursors of soot particles through oligomerization [1][2][3][4][5][6][7][8][9][10][11][12]. The optical and transport properties of PAH clusters are also investigated in the context of organic solar cell design [12][13][14][15][16][17][18][19][20][21]. Carbonaceous compounds involving PAH are studied as pollutants in both environmental and atmospheric science [22][23][24][25][26].…”

DFT Study of the Ambipolar Character of Polymers on the Basis of s-Tetrazine and Aryl Rings

“…34 It must be noted that neither nuclear tunneling effects nor thermal disorder effects have been considered in this model. λ is associated to a geometry relaxation responsible of trapping the charge.…”