On-surface synthesis of square-type porphyrin tetramers with central antiaromatic cyclooctatetraene moiety

0570914 - FZÚ 2024 RIV US eng J - Journal Article
Rascon, E.C. - Riss, A. - Matěj, Adam - Wiengarten, A. - Mutombo, Pingo - Soler Polo, Diego Manuel - Jelínek, Pavel - Auwärter, W.
On-surface synthesis of square-type porphyrin tetramers with central antiaromatic cyclooctatetraene moiety.
Journal of the American Chemical Society. Roč. 145, č. 2 (2023), s. 967-977. ISSN 0002-7863. E-ISSN 1520-5126
R&D Projects: GA ČR(CZ) GX20-13692X; GA MŠMT LM2018110
Grant - others:AV ČR(CZ) AP1601
Program: Akademická prémie - Praemium Academiae
Research Infrastructure: e-INFRA CZ - 90140
Institutional support: RVO:68378271
Keywords : on-surface synthesis * DFT * CAS * SPM
OECD category: Condensed matter physics (including formerly solid state physics, supercond.)
Impact factor: 15, year: 2022
Method of publishing: Limited access
https://doi.org/10.1021/jacs.2c10088

The synthesis of two-dimensionally extended polycyclic heteroatomic molecules keeps attracting considerable attention. In particular, frameworks bearing planar cyclooctatetraenes (COT) moieties can display intriguing properties, including antiaromaticity. Here, we present an on-surface chemistry route to square-type porphyrin tetramers with a central COT ring, coexisting with other oligomers. This approach employing temperature-induced dehydrogenative porphyrin homocoupling in an ultrahigh vacuum environment provides access to surface-supported, unsubstituted porphyrin tetramers that are not easily achievable by conventional synthesis means. Specifically, monomeric free-base (2H-P) and Zn-metalated (Zn-P) porphines (P) were employed to form square type free-base and Zn-functionalized tetramers on Ag(100). An atomic level characterization by bond-resolved atomic force microscopy and scanning tunneling microscopy and spectroscopy is provided, identifying the molecular structures.
Permanent Link: https://hdl.handle.net/11104/0342243