Theoretical investigation on the crystal structures and electron transport properties of several nitrogen-rich pentacene derivatives.

Exploring and synthesizing new simple n-channel organic semiconductor materials with large electron mobility and high air stability have remained a major challenge and hot issue in the field of organic electronics. In the current work, the electron transport properties of four novel nitrogen-rich pentacene derivatives (PBD1, PBD2, PBD3, and PBD4) with two cyano groups as potential n-channel OFET materials have been investigated at the molecular and crystal levels by means of density functional theory (DFT) calculations coupled with the prediction of crystal structures and the incoherent charge-hopping model. Calculations reveal that the studied compounds, which possess low-lying frontier molecular energy levels, large ionization potentials and electron affinities, are very stable exposed to air. Based on predicted crystal structures, the average electron mobility at room temperature (T = 300 K) for PBD1, PBD2, PBD3, and PBD4 is predicted to be as high as 0.950, 0.558, 0.518, and 1.052 cm²·V⁻¹·s⁻¹, which indicate that these four compounds are more than likely to be promising candidates as n-type OFET materials under favorable device conditions. However, this claim needs experimental verification. In addition, the angular-dependent simulation for electron mobility shows that the electron transport is remarkably anisotropic in these molecular crystals and the maximum μ(e) appears along the crystal axis direction since molecules along this direction exhibit the close face-to-face stacking arrangement with short interplanar distances (~3.6-4.0 Å), which induces large electronic couplings.