Pentacene to Octacene: The Limit of Fourfold TIPS-Ethynylation

Abstract

Soluble acenes beyond hexacene are rare. Their sensitivity complicates isolation, purification and application in devices. To increase the stability of acenes, functionalization with trialkylsilylethynyl substituents prevents [4 + 4] dimerization and oxidation. At the same time, such acenes are soluble and processible. Here we present the modular synthesis of fourfold tri-iso-propylsilylethynyl-ethynylated pentacenes to octacenes and investigate their optical and redox properties, frontier orbital positions (CV, density functional theory calculations) as well as their stability in solution (UV/vis, NMR spectroscopy). We also investigated their magnetic properties as a function of acene length. Pentacene, hexacene and heptacene are sufficiently stable to serve as semiconductors in thin-film transistors – the octacene rapidly decays to its butterfly dimer evidence by time-dependent NMR spectroscopy and crystal structure analysis.

Key words

acenes - heptacene - hexacene - octacene - pentacene - polycyclic aromatic hydrocarbons - steric shielding

Publication History

Received: 31 August 2023

Accepted after revision: 04 December 2023

Accepted Manuscript online:
09 January 2024

Article published online:
01 February 2024

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