On-liquid surface synthesis of diyne-linked two-dimensional polymer crystals.

Yang, Ye; Wu, Yufeng; Liu, Chang; Hambsch, Mike; Dong, Tiange; Bodesheim, David; Prasad, Mahabir; Dianat, Arezoo et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

The synthesis of thin crystalline two-dimensional polymers (2DPs) typically relies on reversible dynamic covalent reactions. While substantial progress has been made in solution-based and interfacial syntheses, achieving 2DPs through irreversible carbon-carbon coupling reactions remains a formidable challenge. Herein, we present an on-liquid surface (a mixture of N,N-dimethylacetamide and water, DMAc-H<sub>2</sub>O) synthesis method for constructing diyne-linked 2DP (DY2DP) crystals via Glaser coupling, assisted by a perfluoro-surfactant (PFS) monolayer. In-situ spectroscopic and diffraction techniques reveal that the well-ordered PFS monolayer facilitates the accumulation of Cu<sup>+</sup> ions and subsequent vertical coupling of acetylenic monomers on the DMAc-H<sub>2</sub>O surface. Building on these findings, we successfully synthesized micro-scale rod-shaped DY2DP-Por or graphdiyne (GDY) crystals through the polymerization of porphyrin- or benzene-based monomers, respectively. Our study represents a significant advancement in the field of on-liquid surface chemistry and opens up enormous opportunities for constructing C-C bond linked 2DP crystals with unique functionalities.