Side-group engineering: The influence of norbornadienyl substituents on the properties of ethynylated pentacene and tetraazapentacene

• Introduction of a norbornadienyl substituent in TIPS-PEN and TIPS-TAP.
• Crystal packing, optical, electronic and morphological properties are investigated.
• Improved charge transport for Nor-PEN correlates with increased transfer integrals.
• Nor-TAP exhibits a decreased performance due to smaller LUMO-LUMO interaction.

The chemical modifications of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-PEN) and 6,13-bis(triisopropylsilylethynyl)-5,7,12,14-tetraazapentacene (TIPS-TAP) by introduction of a large norbornadienyl substituent at the silyl atom of the side chain were examined and their effect on the charge transport properties in organic field-effect transistors (OFETs) was investigated. While the introduction of the norbornadienyl substituent resulted in only small changes in the crystallographic packing of these materials and did not affect the optical and electronic properties, the effect on the charge carrier mobility is significant. The hole mobility for the norbornadienyl substituted pentacene (Nor-PEN) is increased compared to similarly prepared TIPS-PEN devices, reaching up to 0.75 cm2/Vs. On the other hand, the electron mobility of the tetraaza derivative (Nor-TAP) is reduced by an order of magnitude compared to its parent TIPS-TAP. The strong effect of the norbornadienyl substitution on the charge carrier mobilities can be explained by the calculation of the transfer integrals and the microstructure of the resulting films of the Nor-derivatives.

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