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Precise control over on-surface covalent reaction pathways is crucial for engineering organic nanostructures with the single-atom precision. Herein, we demonstrate a step-by-step control of an on-surface cascade covalent reaction based on a successive debromination templated by noncovalent metal-organic coordination motifs. The molecular precursor is predesigned with different reactive sites and functional ligands, allowing for both chemical and structural tuning during on-surface reactions. Through the Fe-terpyridine template effect, we are able to direct the reaction to proceed in a three-step cascade pathway and finally to achieve a porous polyarylene nanoribbon structure. The approach opens new opportunities for construction of on-surface organic nanostructures in a predictable manner.

We demonstrate an enhancement of cyclization against polymerization for the on-surface debrominative coupling reaction, by using the metal-organic Cu-N coordination template to direct the reaction pathways. Experiments performed by using ultrahigh-vacuum scanning tunneling microscopy (UHV-STM), with the substitution of metal-coordination centers, metallic substrates and functional organic ligands, corroborate the template effect of the Cu-N coordination., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, we report a fine-tuning of the two-dimensional alkali-pyridyl coordination assemblies facilely realized by surface reaction between tetrapyridyl-porphyrin molecules and alkali halides on Ag(111) under a solventless ultrahigh vacuum condition. High-resolution scanning tunneling topography and X-ray photoelectron spectra reveal the formation of alkali-pyridyl coordination and the induced conformational tuning of the porphyrin macrocycle cores. Furthermore, employing other different alkali halide substitutes, we demonstrate a fine-tuning of the metal-organic nanostructures at the sub-Å scale. Postdeposition of Fe onto the as-formed precursor layer yields a two-dimensional bimetallic framework structure, manifesting a functionalization of the metal-organic interfaces., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)