Facile synthesis of azobenzene‐embedded conjugated macrocycles for optically switchable single‐crystal transistors and tunable supramolecular assemblies

Abstract

AbstractA series of new π‐conjugated macrocycles (AzoM‐n‐E, n = 1–3) incorporating azobenzene units have been synthesized by a facile strategy in one‐pot reaction. The resultant azobenzene‐embedded macrocycles feature intrinsic photoresponsive behaviors and intriguing supramolecular assembling properties. The smallest macrocycle AzoM‐1‐E with a rigid planar conjugated backbone structure is used to prepare the single crystal transistors, showing reversible optical tunability. The moderate size macrocycle AzoM‐2‐E assembles into a dimer in the form of interpenetration through π‐π stacking between azobenzene units. The largest macrocycle AzoM‐3‐E with enhanced flexibility can adaptively assemble with various types of electron‐deficient guests accompanied by distortion of azobenzene. Typically, AzoM‐3‐E assembles with the planar F4‐TCNQ to form a tetragonal geometry by C‐F···π and π‐π interactions, while the assembly with ellipsoidal C70 via π‐π interactions induces AzoM‐3‐E to form a boat‐shaped geometry. This work will shed new light on the development of functional conjugated macrocycles in organic electronics.