Topological Woodward-Hoffmann classification for cycloadditions in polycyclic aromatic azomethine ylides

TL;DR

This paper introduces a topological classification scheme for cycloaddition mechanisms, revealing that exothermic pathways can be topologically forbidden, which is crucial for nanographene synthesis and surface chemistry.

Contribution

It presents a novel topological approach to classify symmetry-forbidden reaction pathways in cycloadditions, integrating reaction modeling with topological analysis.

Findings

Topologically-allowed pathways are endothermic.

Topologically-forbidden pathways are exothermic.

The classification aids in designing cycloadditions for nanographene engineering.

Abstract

The study of cycloaddition mechanisms is central to the fabrication of extended sp2 carbon nanostructures. Reaction modeling in this context has focused mostly on putative, energetically preferred, exothermic products with limited consideration for symmetry allowed or forbidden mechanistic effects. Here, we introduce a scheme for classifying symmetry-forbidden reaction coordinates in Woodward-Hoffmann correlation diagrams. Topological classifiers grant access to the study of reaction pathways and correlation diagrams in the same footing, for the purpose of elucidating mechanisms and products of polycyclic aromatic azomethine ylide (PAMY) cycloadditions with pentacene-yielding polycyclic aromatic hydrocarbons with an isoindole core in the solid-state and on surfaces as characterized by mass spectrometry and scanning tunneling microscopy, respectively. By means of a tight-binding reaction model and density functional theory (DFT) we find topologically-allowed pathways if a product is endothermic, and topologically-forbidden if a product is exothermic. Our work unveils topological classification as a crucial element for reaction modeling for nanographene engineering, and highlights its fundamental role in the design of cycloadditions in on-surface and solid-state chemical reactions, while underscoring that exothermic pathways can be topologically-forbidden.