Understanding the effects of the number of pyrazines and their positions on charge-transport properties in silylethynylated N-heteropentacenes

The charge-transport properties of a series of silylethynylated N-heteropentacenes (TIPS-PEN-xN; x = 2, 4) were systematically investigated using Marcus electron-transfer theory coupled with kinetic Monte Carlo simulations. Electronic structure calculations showed that introducing more pyrazine rings decreases the energy levels of the lowest unoccupied molecular orbitals (LUMOs) and should aid electron transfer. The number and the positions of the pyrazine rings greatly influence the molecular packing in crystals and hence the intermolecular electronic coupling. Furthermore, the introduction of internal (rather than external) pyrazine rings leads to a better charge-transport network. Transport parameters evaluated from the hopping and band-like models both demonstrate that, among the TIPS-PEN-xN molecules, B-TIPS-PEN-4N—which has two internal pyrazine rings—is the most promising n-type material.