Despite a growing understanding of factors that drive monomer self-assembly to form supramolecular polymers, the effects of aromaticity gain have been largely ignored. Herein, we document the aromaticity gain in two different self-assembly modes of squaramide-based bolaamphiphiles. Importantly, O → S substitution in squaramide synthons resulted in supramolecular polymers with increased fiber flexibility and lower degrees of polymerization. Computations and spectroscopic experiments suggest that the oxo- and thiosquaramide bolaamphiphiles self-assemble into "head-to-tail"versus "stacked"arrangements, respectively. Computed energetic and magnetic criteria of aromaticity reveal that both modes of self-assembly increase the aromatic character of the squaramide synthons, giving rise to stronger intermolecular interactions in the resultant supramolecular polymer structures. These examples suggest that both hydrogen-bonding and stacking interactions can result in increased aromaticity upon self-assembly, highlighting its relevance in monomer design.@en

This study aims to identify photo-/electrocatalysts that can enhance the oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR), which are of utmost importance in electro-/photochemical energy systems, such as solar energy, fuel cells, water electrolyzers, or metal-air batteries. Our study focused on investigating the 2D Ge₂Se₂P₄ monolayer and found that it exhibits a bifunctional photocatalyst with a very high solar-to-hydrogen efficiency. The two-dimensional (2D) Ge₂Se₂P₄ monolayer has superior HER activity compared to that of most 2D materials, and it also outperforms the reference catalysts IrO₂(110) and Pt(111) in terms of low overpotential values for ORR and OER mechanisms. Such superior catalytic performance in the 2D Ge₂Se₂P₄ monolayer can be attributed to its electron states, charge transfer process, and suitable band alignments referring to normal hydrogen electrodes. Overall, the study suggests that the Ge₂Se₂P₄ monolayer could be an excellent bifunctional catalyst for advancing photo-/electrochemical energy systems.

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