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π-conjugated molecules are viewed as fundamental components in forthcoming molecular nanoelectronics, in which semiconducting functional units are linked to each other via metallic molecular wires. However, it is still challenging to construct such block cooligomers on surface. Here, we present a synthesis of [18]-polyene linked Zn-porphyrin cooligomers via two-step reaction of the alkyl groups on Cu(111) and Cu(110). Nonyl groups (-C9H19) substituted at the 5,15-meso positions of Zn-porphyrin were first transformed to alkenyl groups (-C9H10) by dehydrogenation. Subsequently, homocoupling of the terminal -CH2 groups resulted in the formation of extended [18]-polyene linked porphyrin cooligomers. The structures of products at each reaction step were investigated by bond-resolved scanning tunneling microscopy at low temperature. A combination of angle-resolved photoemission spectroscopy and density functional theory calculations revealed the metallic property of the all trans [18]-polyene linker on Cu(110). This finding may provide an approach to fabricate complex nano-carbon structures on surface.

Description:

π-conjugated molecules are viewed as fundamental components in forthcoming molecular nanoelectronics, in which semiconducting functional units are linked to each other via metallic molecular wires. However, it is still challenging to construct such block cooligomers on surface. Here, we present a synthesis of [20]-polyene linked Zn-porphyrin cooligomers via two-step reaction of the alkyl groups on Cu(111) and Cu(110). Nonyl groups (-C9H19) substituted at the 5,15-meso positions of Zn-porphyrin were first transformed to alkenyl groups (-C9H10) by dehydrogenation. Subsequently, homocoupling of the terminal -CH2 groups resulted in the formation of extended [20]-polyene linked porphyrin cooligomers. The structures at each reaction step and the aromaticity of Zn-porphyrin core were investigated by bond-resolved scanning tunneling microscopy at low temperature. A combination of angle-resolved photoemission spectroscopy and density functional theory calculations revealed the metallic property of the all trans [20]-polyene linker. This finding may provide an approach to fabricate complex nano-carbon structures on surface.

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• In Copyright
  This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Nano, copyright © 2024 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsnano.3c12849

Keyword: On-surface synthesis, [18]-polyene linked Zn-porphyrin cooligomers, scanning tunneling microscopy, angle-resolved photoemission spectroscopy, density functional theory calculations

Date published: 2024-05-28

Publisher: American Chemical Society (ACS)

Journal:

• ACS Nano (ISSN: 1936086X) vol. 18 issue. 21 p. 13551-13559

Funding:

• Japan Society for the Promotion of Science JP20H05621
• Japan Society for the Promotion of Science JP22H00285
• Japan Society for the Promotion of Science JP22H01957
• National Institute for Materials Science

Manuscript type: Author's version (Accepted manuscript)

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First published URL: https://doi.org/10.1021/acsnano.3c12849

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Updated at: 2024-06-19 16:17:37 +0900

Published on MDR: 2025-05-17 08:20:47 +0900