AI Article Synopsis
- - The study explores the Ullmann coupling method for synthesizing functional materials, focusing on understanding the elemental binding energy shifts and the role of atomic hydrogen.
- - It finds that changes in the work function, rather than just the formation of new carbon-silver bonds, are key to shifts in carbon binding energy during the reaction process.
- - The research also shows that atomic hydrogen can decompose organometallic chains while promoting hydrogenation in covalent structures, indicating its dual effects in modifying surface chemistry during Ullmann coupling.
Article Abstract
The Ullmann coupling of aryl halides is a powerful method in the on-surface synthesis of functional materials. Understanding its basic aspects and influencing factors can aid in the use of this tool for the fabrication of intriguing structures. In this study, we unveil (1) the origin of the shift in the elemental binding energy (BE) and (2) the functions of atomic hydrogen (AH) in a typical Ullmann coupling system using combined spectroscopy and microscopy techniques. During debromination of the aryl halide precursor, the work function (WF) alteration is correlated with the surface Br amount. The WF change instead of C-Ag formation is proposed to play a dominant role in the shift of the molecular C 1s BE. AH dosing onto organometallic chains leads to chain decomposition and surface Br removal. In contrast, AH dosing onto covalent poly(phenylene) (PPP) chains results in superhydrogenation in addition to Br removal. The C 1s BE shift is attributed to both WF change and superhydrogenation effects. Thermal annealing restores the PPP chains by eliminating superhydrogenation, which causes the C 1s BE to shift to a high BE. This study provides deep insights into the mechanisms of Ullmann coupling on surfaces, highlighting the significant role of WF alterations and AH treatments in these processes.
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