DNA-Enforced Conformational Restriction of an Atropisomer

Abstract

We report the conformational restriction of a freely rotating biaryl derivative resulting in strong exciton coupled circular dichroism between the two nondegenerate fragments of the dyad NP only in the presence of DNA. The napthalenimide–perylenimide dyad NP, an extended 1,1′-binaphthalene derivative, has a rotational barrier of 100 kJ/mol, leading to fast racemization. While end-stacking with a DNA hairpin, NP exhibits a significantly high rotational barrier, an additional 91 kJ/mol, resulting in atroposelective preference. Such reversible conformational constraints using biotemplates show huge potential toward conformational analysis, dynamic kinetic resolution, and asymmetric synthesis. The present work focuses on conformational analysis of a freely rotating biaryl derivative using a combination of techniques such as temperature-dependent UV–vis, circular dichroism, steady-state and time-resolved fluorescence spectroscopy, and molecular dynamics simulation.