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The first step toward functional supramolecules is to reveal the self-assembly mechanism on surfaces. Here, we report the molecular self-assembly of one of the simplest functionalized benzene molecules, hexahydroxybenzene, on the Au(111) surface studied by low temperature scanning tunneling microscopy. Besides the normal hexagonal phase, we observe a new square lattice. The intact gold herringbone structure after adsorption indicates the weak molecule\u2013substrate interaction. According to the shared domain boundary between such two phases, the detailed molecular orientation and lattice location with hydrogen bonding can be deduced. Subsequent annealing can then convert these phases into a new molecular striped phase with a much smaller lattice constant. Our study here shows the rich structures when the self-assembly formation occurs at surfaces.<\/jats:p>","DOI":"10.1063\/5.0291695","type":"journal-article","created":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T10:27:52Z","timestamp":1760005672000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":1,"title":["Supramolecular self-assemblies of hexahydroxybenzene on Au(111)"],"prefix":"10.1063","volume":"163","author":[{"ORCID":"https:\/\/orcid.org\/0009-0001-2902-0131","authenticated-orcid":false,"given":"Talha","family":"Ijaz","sequence":"first","affiliation":[{"name":"Vacuum Interconnected Nanotech Workstation (Nano-X), Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences (CAS) 1 , Suzhou 215123,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ling","family":"Zhang","sequence":"additional","affiliation":[{"name":"Vacuum Interconnected Nanotech Workstation (Nano-X), Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences (CAS) 1 , Suzhou 215123,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yingying","family":"Zhang","sequence":"additional","affiliation":[{"name":"Vacuum Interconnected Nanotech Workstation (Nano-X), Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences (CAS) 1 , Suzhou 215123,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lianlian","family":"Ji","sequence":"additional","affiliation":[{"name":"Vacuum Interconnected Nanotech Workstation (Nano-X), Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences (CAS) 1 , Suzhou 215123,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9268-3595","authenticated-orcid":false,"given":"Yiyao","family":"Chen","sequence":"additional","affiliation":[{"name":"Vacuum Interconnected Nanotech Workstation (Nano-X), Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences (CAS) 1 , Suzhou 215123,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aixi","family":"Chen","sequence":"additional","affiliation":[{"name":"Vacuum Interconnected Nanotech Workstation (Nano-X), Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences (CAS) 1 , Suzhou 215123,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9233-0650","authenticated-orcid":false,"given":"Fang-Sen","family":"Li","sequence":"additional","affiliation":[{"name":"Vacuum Interconnected Nanotech Workstation (Nano-X), Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences (CAS) 1 , Suzhou 215123,","place":["China"]},{"name":"School of Nano-Tech and Nano-Bionics, University of Science and Technology of China 2 , Hefei 230026,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2025,10,9]]},"reference":[{"key":"2025100906274622400_c1","doi-asserted-by":"publisher","first-page":"416","DOI":"10.1021\/acs.accounts.0c00652","article-title":"Exotic topological bands and quantum states in metal\u2013organic and covalent\u2013organic frameworks","volume":"54","year":"2021","journal-title":"Acc. 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