Syntheses, characterizations and reactions of acene-2,3-dicarbaldehydes

Abstract

Here, we report improved syntheses, detailed characterizations and reactions of a series of acene-2,3-dicarbaldehydes including tetracene-2,3-dicarbaldehyde. DFT calculations corroborate and complement the experimental results. Tetracene-2,3-dicarbaldehyde and the benchmark organic semiconductor pentacene have isoelectronic π-systems and similar HOMO–LUMO gaps. Tetracene-2,3-dicarbaldehyde is soluble in a host of organic solvents (e.g., DMF, toluene, THF, chloroform, dichloromethane) and shows excellent photooxidative resistance in solution phases exposed to light and air. Further, it is readily sublimed from the solid-state without decomposition, and can be functionalized using different chemistries. We have demonstrated the utility of acene-2,3-dicarbaldehydes as reactants in the syntheses of novel α,α′-diaryl-2,3-acenedimethanols and acenotropones via Grignard reactions and double-aldol condensation reactions, respectively. The acenotropones were further reacted with concentrated H₂SO₄ to generate hydroxyacenotropylium ions that exhibit long wavelength absorption in the visible and near-IR regions. The optical gap measured for hydroxyanthracenotropylium ion is 1.3 eV. The results gained here implicate acene-2,3-dicarbaldehydes as potential high-value organic semiconductors and as precursors to a host of interesting molecules and materials.