Expanded phthalocyanines are a promising class of materials for optoelectronic applications, owing to their unique properties and versatile metal coordination reactivity. The expansion of their π-electron systems and resulting red-shifted absorption are of particular interest for achieving broader applications. Here, we report the on-surface synthesis of metallo-phthalocyanines with extended electron systems and an open-chain polycyanine from ortho-dicarbonitrile precursors on Ag(111) and Au(111), studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The larger 6,7-di(2-naphthyl)-2,3-naphthalenedicarbonitrile (NND) undergoes spontaneous cyclotetramerization on the Ag(111) surface forming the corresponding silver naphthalocyanines (Ag-NPc), contrasting previous reports where a partially aliphatic ortho-dicarbonitrile precursor formed polycyanine chains. In contrast, monolayers of the smaller 6,7-diphenyl-2,3-naphthalenedicarbonitrile (PND) form the corresponding naphthalocyanine only in the presence of co-adsorbed iron atoms (Fe-NPc). In the absence of iron, PND multilayers form polycyanine chains and Ag-NPc. NND and PND further differ in their reactivity due to the supramolecular behavior of their products. While the larger Ag-NPc aggregates to non-covalent one-dimensional ribbons, the smaller Fe-NPc forms an extended non-covalent two-dimensional network. Our study demonstrates the versatility of on-surface dinitrile tetramerization for the synthesis of π-extended cyclic phthalocyanines and their open-chain polycyanine counterparts.

Lukas J. Heuplick

Qitang Fan

Dmitriy A. Astvatsaturov

Tatiana V. Dubinina

J. Michael Gottfried

Communications Chemistry

COMMUNICATIONS CHEMISTRY 是 NATURE RESEARCH 的一本开放获取期刊，发表化学科学所有领域的高质量研究、评论和评论。该杂志发表的研究论文代表了重大进展，为专业研究领域带来了新的化学见解。我们还旨在为所有化学家的重要问题提供一个社区论坛，无论其子学科如何。

Communications Chemistry is an open-access journal published by NATURE RESEARCH, dedicated to high-quality research, reviews, and commentaries across all areas of chemical science. The research papers published in this journal represent significant advancements, providing new insights into the field of chemistry. We also aim to offer a community forum for all chemists to discuss important issues, regardless of their sub-discipline.

《Communications Chemistry》是NATURE RESEARCH旗下的一本开放获取期刊，致力于发表化学科学各个领域的高质量研究论文、评论和综述。该期刊所刊登的研究成果代表了重要的科学进展，为专业领域带来了新的化学见解。此外，我们还旨在为所有化学家提供一个讨论重要问题的社区论坛，无论其研究的子学科是什么。

Category	Quartile
化学	2
化学, 化学综合	2

On-surface synthesis of phthalocyanines with extended π-electron systems

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Journal Info

Category	Quartile
CHEMISTRY, MULTIDISCIPLINARY	1