Synthetic chiral molecular nanographenes: the key figure of the racemization barrier

Abstract

Chirality is one of the most intriguing concepts of chemistry, involving living systems and, more recently, materials science. In particular, the bottom-up synthesis of molecular nanographenes endowed with one or several chiral elements is a current challenge for the chemical community. The wilful introduction of defects in the sp² honeycomb lattice of molecular nanographenes allows the preparation of chiral molecules with tuned band-gaps and chiroptical properties. There are two requirements that a system must fulfill to be chiral: (i) lack of inversion elements (planes or inversion centres) and (ii) to be configurationally stable. The first condition is inherently established by the symmetry group of the structure, however, the limit between conformational and configurational isomers is not totally clear. In this feature article, the chirality and dynamics of synthetic molecular nanographenes, with special emphasis on their racemization barriers and, therefore, the stability of their chiroptical properties are discussed. The general features of nanographenes and their bottom-up synthesis, including the main defects inducing chirality in molecular nanographenes are firstly discussed. In this regard, the most common topological defects of molecular NGs as well as the main techniques used for determining their energy barriers are presented. Then, the manuscript is structured according to the dynamics of molecular nanographenes, classifying them in four main groups, depending on their respective isomerization barriers, as flexible, detectable, isolable and rigid nanographenes. In these sections, the different strategies used to increase the isomerization barrier of chiral molecular nanographenes that lead to configurationally stable nanographenes with defined chiroptical properties are discussed.