# On-Surface Synthesis of Polyene-Linked Porphyrin Cooligomer https://mdr.nims.go.jp/datasets/2c791b17-69c6-44b7-880f-e851b4ba2639 ## File - [ACS_Cooligomer_SI_Rev2 - Copy.docx](https://mdr.nims.go.jp/filesets/ef071056-a67a-4fb9-806b-0b7413227e6d/download) ([Detail](https://mdr.nims.go.jp/filesets/ef071056-a67a-4fb9-806b-0b7413227e6d.md)) - [ACS_Cooligomer_Main_Rev2 - Copy.docx](https://mdr.nims.go.jp/filesets/8439a1bf-226a-4188-b1f8-95800563a2bb/download) ([Detail](https://mdr.nims.go.jp/filesets/8439a1bf-226a-4188-b1f8-95800563a2bb.md)) ## Id 2c791b17-69c6-44b7-880f-e851b4ba2639 ## Local identifier ## Visibility open_to_public ## State published ## Created at 2024-06-04T04:05:48.232569Z ## Updated at 2025-05-16T23:30:10.426222Z ## Published at 2025-05-16T23:20:47.494533Z ## Doi https://doi.org/10.48505/nims.4534 ## First published url https://doi.org/10.1021/acsnano.3c12849 ## Date published 2024-05-28 ## Recorded date published 2024-5-28 ## Resource type journal_article ## Manuscript type accepted_manuscript ## Collection ## Title - title: On-Surface Synthesis of Polyene-Linked Porphyrin Cooligomer title_type: original lang: en ## Description - 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 [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_type: abstract lang: en - 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. description_type: abstract lang: und ## Creator - name: Kewei Sun role: author orcid: https://orcid.org/0000-0002-1835-243X organization: National Institute for Materials Science department: International Center for Young Scientists ror: https://ror.org/026v1ze26 - name: Atsushi Ishikawa role: author orcid: https://orcid.org/0000-0001-6908-831X organization: Tokyo Institute of Technology department: Department of Transdisciplinary Science and Engineering - name: Ryota Itaya role: author organization: Osaka University department: Department of Applied Physics - name: Yuichiro Toichi role: author organization: Osaka University department: Department of Applied Physics - name: Takuya Yamakado role: author organization: Kyoto University department: Graduate School of Science - name: Atsuhiro Osuka role: author organization: Kyoto University department: Graduate School of Science - name: Takayuki Tanaka role: author organization: Kyoto University department: Graduate School of Science - name: Kazuyuki Sakamoto role: author organization: Osaka University department: Department of Applied Physics - name: Shigeki Kawai role: author orcid: https://orcid.org/0000-0003-2128-0120 organization: National Institute for Materials Science department: Center for Basic Research on Materials ror: https://ror.org/026v1ze26 ## Contact agent ## Publisher organization: American Chemical Society (ACS) ## Managing organization ## Keyword - subject: On-surface synthesis schema: not_defined - subject: "[18]-polyene linked Zn-porphyrin cooligomers" schema: not_defined - subject: scanning tunneling microscopy schema: not_defined - subject: angle-resolved photoemission spectroscopy schema: not_defined - subject: density functional theory calculations schema: not_defined ## Rights - description: 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 identifier: http://rightsstatements.org/vocab/InC/1.0/ ## Other identifier(s) ## Data origin - data_origin_type: other ## Embargo start_date: 2024-05-17 end_date: 2025-05-17 ## Journal - title: ACS Nano issn: 1936086X volume: '18' issue: '21' start_page: 13551 end_page: 13559 ## Conference ## Related item ## Funding - identifier: JP20H05621 funder_name: Japan Society for the Promotion of Science - identifier: JP22H00285 funder_name: Japan Society for the Promotion of Science - identifier: JP22H01957 funder_name: Japan Society for the Promotion of Science - funder_name: National Institute for Materials Science ## Instrument ## Instrument operator ## Instrument managing organization ## Measurement method ## Specimen ## Chemical composition ## Structure for specimen ## Structural feature for specimen ## Specific property for specimen ## Process for specimen treatment ## Computational method ## Energy level/transition state ## Software ## Custom property ## Fileset - id: ef071056-a67a-4fb9-806b-0b7413227e6d filename: ACS_Cooligomer_SI_Rev2 - Copy.docx content_type: application/vnd.openxmlformats-officedocument.wordprocessingml.document size: 5109400 md5: 3ee0f509584b3d0c156f922a570f4701 - id: 8439a1bf-226a-4188-b1f8-95800563a2bb filename: ACS_Cooligomer_Main_Rev2 - Copy.docx content_type: application/vnd.openxmlformats-officedocument.wordprocessingml.document size: 4313166 md5: b987cd3c8e52a2dac748eacf3d9915f8 ## Thumbnail fileset_id: 8439a1bf-226a-4188-b1f8-95800563a2bb filename: ACS_Cooligomer_Main_Rev2 - Copy.docx