[2,2](5,8)Picenophanedienes: Syntheses, Structural Analyses, Molecular Dynamics, and Reversible Intramolecular Structure Conversion

Abstract

This study presents an important and efficient synthetic approach to 5,8-dibromo-2,11-di<i>-tert-</i>butylpicene (<b>3</b>), with multigram scale, which was then converted to a new series of picenophanes (<b>6</b>-<b>10</b>). The tub-shaped [2,2](5,8)picenophanediene <b>8</b> with two <i>cis</i>-ethylene linkers was explored using X-ray crystallography. The tub-to-tub inversion proceed through the successive bending of the linkers and the barrier for isopropyl-substituted derivative <b>10</b> was experimentally estimated to be 18.7 kcal/mol. Picenophanes with a large π-system and semi-rigid structure exhibited anomalous photophysical properties. The ethano-bridged picenophane shows the weak exciton delocalization while the <i>cis</i>-ethylene-bridged picenophane exhibits dual emission rendered by the weakly delocalized exciton and excimer. With the aid of the ultrafast time-resolved emission spectroscopy, the mechanism of the excimer formation is resolved, showing a unique behavior of two-state reversible reaction with fast structural deformation whose lifetime is around 20 ps at 298 K. This work demonstrates that the slight difference in the bridge of tub-shaped picenophanes renders distinct photophysical behavior, revealing the potential of harnessing inter-moiety reaction in the picenophane systems.