Critical role of phenyl substitution and catalytic substrate on the surface-assisted polymerization of dibromobianthracene derivatives

TL;DR

This study systematically explores how phenyl substitution and the choice of catalytic metal surface influence the on-surface polymerization pathways of dibromobianthracene derivatives, leading to diverse nanostructures.

Contribution

It reveals how a single precursor can produce various polymers and nanostructures depending on the catalytic substrate and molecular design, advancing on-surface synthesis control.

Findings

Different substrates yield distinct polymer structures.

Phenyl substitution significantly alters reaction pathways.

Precise control over nanostructure formation achieved.

Abstract

Understanding the nature and hierarchy of on surface reactions is a major chal- lenge for designing coordination and covalent nanostructures by means of multistep synthetic routes. In particular, intermediates and final products are hard to predict since reaction paths and their activation windows depend on the choice of both the molecular precursor design and the substrate. Here we report a systematic study of the effect of the catalytic metal surface to reveal how a single precursor can give rise to very distinct polymers that range from coordination and covalent non planar polymer chains of distinct chirality, to atomically precise graphene nanoribbons and nanoporous graphene. Our precursor consists on adding two phenyl substituents to 10,10'-dibromo 9,9'-bianthracene, a well-studied precursor in the on-surface synthesis of graphene nanoribbons. The critical role of the monomer design on the reaction paths is inferred from the fact that the phenyl substitution leads to very distinct products in each one of the studied metallic substrates.