journal article·2023-07-25

Highly Regioselective Cyclodehydrogenation of Diphenylporphyrin on Metal Surfaces

Yong Zhang, Jianchen Lu, Hangjing Zhou, Guang Zhang, Zilin Ruan, Yi Zhang, Hui Zhang, Shijie Sun, Geifei Niu, Boyu Fu, Bing Yang, Long Chen, Lei Gao, Jinming Cai

ACS Nano· Volume 17· Issue 14
Publisher page

Abstract

Exploring the effect of porphin tautomerism on the regioselectivity of its derivatives is a big challenge, which is significant for the development and application of porphyrin drugs. In this work, we demonstrate the regioselectivity of 2 H -diphenylporphyrin (H 2 -DPP) in the planarization reaction on Au(111) and Ag(111) substrates. H 2 -DPP monomer forms two configurations ( anti- and syn- ) via a dehydrogenation coupling, between which the yield of the anti -configuration exceeds 90%. Using high-resolution scanning tunneling microscopy, we visualize the reaction processes from the H 2 -DPP monomer to the final two planar products. Combined with DFT calculations of the potential reaction pathway and comparative experiments on Au(111) and Ag(111) substrates. Using M-DPP (M = Cu and Fe), we confirm that the regioselectivity of H 2 -DPP is derived from the reaction energy barrier during the cyclodehydrogenation reaction of different tautomers. This work reveals the regioselectivity mechanism of H 2 -DPP on the atomic scale, which holds great significance for understanding the chemical conversion process of organic macrocyclic molecules.
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Research context

OpenAlex topics: Surface Chemistry and Catalysis · Porphyrin and Phthalocyanine Chemistry · Molecular Junctions and Nanostructures

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China

Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, Tianjin 300072, China

CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, the Chinese Academy of Sciences, Dalian 116023, China

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China

Faculty of Science, Kunming University of Science and Technology, Kunming 650500, China

Funding

Kunming University of Science and Technology · National Natural Science Foundation of China · Chinese Academy of Sciences · Graphene Application and Engineering Research Center, Education Department of Yunnan Province · Yunnan Innovation Team of Graphene Mechanism Research and Application Industrialization · Yunnan

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