Kinetically stabilized 1,3-diarylisobenzofurans and the possibility of preparing large, persistent isoacenofurans with unusually small HOMO-LUMO gaps.

Abstract

DFT calculations demonstrate that an isoacenofuran of any size possesses a smaller HOMO-LUMO gap than the corresponding acene bearing an isoelectronic π-system (i.e., the same total number of rings). Isoacenofurans show limited stability due in part to the highly reactive 1,3-carbons of the furan ring. Both 1,3-dimesitylisobenzofuran and 1,3-di(2',4',6'-triethylphenyl)isobenzofuran, each bearing sterically congesting ortho-alkyl groups on their phenyl substituents, have been synthesized and shown to adopt non-planar conformations with the ortho-alkyl groups located above and below the most reactive 1,3-carbons of the furan ring. These bulky substituents provide a strong measure of kinetic stabilization. Thus, 1,3-dimesitylisobenzofuran and 1,3-di(2',4',6'-triethylphenyl)isobenzofuran are significantly less reactive than 1,3-diphenylisobenzofuran toward the strong dienophiles DMAD and acrylonitrile. The insights gained here suggest that the synthesis of large, persistent, kinetically stabilized isoacenofurans with unusually small HOMO-LUMO gaps is achievable. As such, these molecules deserve increased attention as potential p-type organic semiconductors.