{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,26]],"date-time":"2026-03-26T14:18:56Z","timestamp":1774534736717,"version":"3.50.1"},"reference-count":42,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2026,3,26]],"date-time":"2026-03-26T00:00:00Z","timestamp":1774483200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Natural Science Foundation of China\n\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t              https:\/\/ror.org\/01h0zpd94","award":["11774039"],"award-info":[{"award-number":["11774039"]}]},{"name":"National Natural Science Foundation of China\n\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t              https:\/\/ror.org\/01h0zpd94","award":["11874304"],"award-info":[{"award-number":["11874304"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Nanomaterials"],"abstract":"<jats:p>The two-dimensional chiral self-assembly and chiral separation of achiral Ext-TEB molecules on a Bi(111) surface were investigated using low-temperature scanning tunneling microscopy (LT-STM). At low coverage, the molecules self-assembled into chiral clusters. As the coverage increased, a monolayer film with a non-edge-sharing honeycomb structure was formed. This supramolecular structure exhibited organizational chirality, accompanied by chiral separation. Upon annealing, part of the non-edge-sharing honeycomb structure transformed into a close-packed structure, while retaining the organizational chirality, supramolecular chirality, and pronounced chiral separation. Furthermore, applying a higher bias was found to induce a transition in the electronic state of the non-edge-sharing honeycomb structure, converting it into an edge-sharing honeycomb configuration. This study reveals that the chirality of 1,3,5-tris(4-ethynylphenyl) benzene (Ext-TEB) arises from the rotation of the side-chain phenyl rings, which is induced by the rotation of the molecular axis relative to the substrate lattice. This work presents a strategy for the preparation of chiral nanostructures from achiral molecules due to the spontaneous chiral symmetry generation.<\/jats:p>","DOI":"10.3390\/nano16070399","type":"journal-article","created":{"date-parts":[[2026,3,26]],"date-time":"2026-03-26T13:37:15Z","timestamp":1774532235000},"page":"399","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Chiral Self-Assembly and Chiral Separation of Ext-TEB Molecules on Bi(111)"],"prefix":"10.3390","volume":"16","author":[{"given":"Lei","family":"Liu","sequence":"first","affiliation":[{"name":"International Joint Laboratory for Light Alloys (MOE), College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zheng","family":"Wei","sequence":"additional","affiliation":[{"name":"International Joint Laboratory for Light Alloys (MOE), College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Min-Long","family":"Tao","sequence":"additional","affiliation":[{"name":"School of Physical Science and Technology, Southwest University, Chongqing 400715, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kai","family":"Sun","sequence":"additional","affiliation":[{"name":"School of Physical Science and Technology, Southwest University, Chongqing 400715, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ming-Xia","family":"Shi","sequence":"additional","affiliation":[{"name":"Key Laboratory for Electronic Materials, College of Electrical Engineering, Northwest Minzu University, Lanzhou 730030, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1311-3736","authenticated-orcid":false,"given":"Jun-Zhong","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Physical Science and Technology, Southwest University, Chongqing 400715, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2026,3,26]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"5901","DOI":"10.1021\/jacs.3c11882","article-title":"Altering Spin Distribution of Tb2Pc3 via Molecular Chirality Manipulation","volume":"146","author":"Liao","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"2308233","DOI":"10.1002\/smll.202308233","article-title":"Spin-Selective Electron Transport Through Single Chiral Molecules","volume":"20","author":"Safari","year":"2024","journal-title":"Small"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"14417","DOI":"10.1021\/jacs.1c05949","article-title":"Packing Biomolecules into Sierpinski Triangles with Global Organizational Chirality","volume":"143","author":"Li","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Katrivas, L., Makarovsky, A., Kempinski, B., Randazzo, A., Improta, R., Rotem, D., Porath, D., and Kotlyar, A.B. (2024). Ag+-Mediated Folding of Long Polyguanine Strands to Double and Quadruple Helixes. Nanomaterials, 14.","DOI":"10.3390\/nano14080663"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"3958","DOI":"10.1021\/acsnano.2c12720","article-title":"Chirality-Specific Unidirectional Rotation of Molecular Motors on Cu(111)","volume":"17","author":"Schied","year":"2023","journal-title":"ACS Nano"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1038\/s41467-024-55405-5","article-title":"An aperiodic chiral tiling by topological molecular self-assembly","volume":"16","author":"Voigt","year":"2025","journal-title":"Nat. Commun."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"3171","DOI":"10.1021\/ja2106652","article-title":"Induction of Chirality in an Achiral Monolayer at the Liquid\/Solid Interface by a Supramolecular Chiral Auxiliary","volume":"134","author":"Cat","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"2207209","DOI":"10.1002\/smll.202207209","article-title":"Solvent Mediated Nanoscale Quasi-Periodic Chirality Reversal in Self-Assembled Molecular Networks Featuring Mirror Twin Boundaries","volume":"19","author":"Yamagata","year":"2023","journal-title":"Small"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"10357","DOI":"10.1021\/acsnano.7b05314","article-title":"Conformation Manipulation and Motion of a Double Paddle Molecule on an Au(111) Surface","volume":"11","author":"Soe","year":"2017","journal-title":"ACS Nano"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"8435","DOI":"10.1021\/acs.chemrev.8b00770","article-title":"Main-Group-Based Electro- and Photoactive Chiral Materials","volume":"119","author":"Pop","year":"2019","journal-title":"Chem. Rev."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"112","DOI":"10.1038\/nmat1558","article-title":"Chiral switching by spontaneous conformational change in adsorbed organic molecules","volume":"5","author":"Weigelt","year":"2006","journal-title":"Nat. Mater."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"081602","DOI":"10.1063\/1.3685713","article-title":"Chiral recognition of zinc phthalocyanine on Cu(100) surface","volume":"100","author":"Chen","year":"2012","journal-title":"Appl. Phys. Lett."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"074705","DOI":"10.1063\/1.3314725","article-title":"Self-assembly of enantiopure domains: The case of indigo on Cu(111)","volume":"132","author":"Villagomez","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"4691","DOI":"10.1039\/c3cp44239j","article-title":"Alternating chirality in the monolayer H2TPP on Cu(110)-(2 \u00d7 1)O","volume":"15","author":"Wagner","year":"2013","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1395","DOI":"10.1021\/nl050717q","article-title":"Losing the expression of molecular chirality in self-assembled physisorbed monolayers","volume":"5","author":"Zhang","year":"2005","journal-title":"Nano Lett."},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Safari, M.R., Matthes, F., Ernst, K.H., B\u00fcrgler, D.E., and Schneider, C.M. (2022). Deposition of Chiral Heptahelicene Molecules on Ferromagnetic Co and Fe Thin-Film Substrates. Nanomaterials, 12.","DOI":"10.3390\/nano12193281"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"2140","DOI":"10.1021\/acs.accounts.5b00174","article-title":"On-Surface Synthesis of Carbon-Based Scaffolds and Nanomaterials Using Terminal Alkynes","volume":"48","author":"Klappenberger","year":"2015","journal-title":"Acc. Chem. Res."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1702428","DOI":"10.1002\/adma.201702428","article-title":"Conjugated Microporous Polymer Nanosheets for Overall Water Splitting Using Visible Light","volume":"29","author":"Wang","year":"2017","journal-title":"Adv. Mater."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"2251","DOI":"10.1021\/nl403791q","article-title":"Local Electronic and Chemical Structure of Oligo-acetylene Derivatives Formed Through Radical Cyclizations at a Surface","volume":"14","author":"Riss","year":"2014","journal-title":"Nano Lett."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"11200","DOI":"10.1039\/C4CC02859G","article-title":"Cyclotrimerization of arylalkynes on Au(111)","volume":"50","author":"Liu","year":"2014","journal-title":"Chem. Commun."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"5087","DOI":"10.1021\/jacs.8b13547","article-title":"Synthesizing Highly Regular Single-Layer Alkynyl\u2013Silver Networks at the Micrometer Scale via Gas-Mediated Surface Reaction","volume":"141","author":"Zhang","year":"2019","journal-title":"J. Am. Chem. Soc."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"3030","DOI":"10.1038\/s41467-024-47252-1","article-title":"Universal inter-molecular radical transfer reactions on metal surfaces","volume":"15","author":"Wang","year":"2024","journal-title":"Nat. Commun."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1286","DOI":"10.1038\/ncomms2291","article-title":"Homo-coupling of terminal alkynes on a noble metal surface","volume":"3","author":"Zhang","year":"2012","journal-title":"Nat. Commun."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"3987","DOI":"10.1021\/jp310606r","article-title":"Steering On-Surface Self-Assembly of High-Quality Hydrocarbon Networks with Terminal Alkynes","volume":"117","author":"Zhang","year":"2013","journal-title":"J. Phys. Chem. C"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"9669","DOI":"10.1021\/acs.jpcc.5b02955","article-title":"Unusual Deprotonated Alkynyl Hydrogen Bonding in Metal-Supported Hydrocarbon Assembly","volume":"119","author":"Zhang","year":"2015","journal-title":"J. Phys. Chem. C"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"191","DOI":"10.1016\/j.progsurf.2006.03.001","article-title":"The surfaces of bismuth: Structural and electronic properties","volume":"81","author":"Hofmann","year":"2006","journal-title":"Prog. Surf. Sci."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"113102","DOI":"10.1103\/PhysRevB.67.113102","article-title":"Electronic structure of a bismuth bilayer","volume":"67","author":"Ast","year":"2003","journal-title":"Phys. Rev. B"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"277","DOI":"10.1016\/j.jpcs.2019.01.027","article-title":"Dependence of the band structure of Bi(111) bilayers on lattice constant and spin-orbit splitting induced by a H monolayer","volume":"129","author":"Yakovkin","year":"2019","journal-title":"Phys. Chem. Solids"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"2300207","DOI":"10.1002\/sstr.202300207","article-title":"Achieving a Large Energy Gap in Bi(110) Atomically Thin Films","volume":"4","author":"Yuan","year":"2023","journal-title":"Small Struct."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"016801","DOI":"10.1103\/PhysRevLett.109.016801","article-title":"Spatial and Energy Distribution of Topological Edge States in Single Bi(111) Bilayer","volume":"109","author":"Yang","year":"2012","journal-title":"Phys. Rev. Lett."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"031602","DOI":"10.1063\/1.4927206","article-title":"One-dimensional edge state of Bi thin film grown on Si(111)","volume":"107","author":"Kawakami","year":"2015","journal-title":"Appl. Phys. Lett."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"145644","DOI":"10.1016\/j.apsusc.2020.145644","article-title":"One dimensional electronic states in mirror twin boundaries of Bi (1 1 1)","volume":"512","author":"Qin","year":"2020","journal-title":"Appl. Surf. Sci."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"045428","DOI":"10.1103\/PhysRevB.77.045428","article-title":"First-principles investigation of structural and electronic properties of ultrathin Bi films","volume":"77","author":"Koroteev","year":"2008","journal-title":"Phys. Rev. B"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"256106","DOI":"10.1103\/PhysRevLett.95.256106","article-title":"Role of Surface Electronic Structure in Thin Film Molecular Ordering","volume":"95","author":"Thayer","year":"2005","journal-title":"Phys. Rev. Lett."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"073109","DOI":"10.1063\/1.1865350","article-title":"Thin bismuth film as a template for pentacene growth","volume":"86","author":"Sadowski","year":"2005","journal-title":"Appl. Phys. Lett."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"054717","DOI":"10.1063\/5.0247758","article-title":"Growth of crystalline thin films of picene on semimetallic Bi(111) surface","volume":"162","author":"Fu","year":"2025","journal-title":"J. Chem. Phys."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"6388","DOI":"10.1038\/s41467-022-34187-8","article-title":"Spin-orbital Yu-Shiba-Rusinov states in single Kondo molecular magnet","volume":"13","author":"Xia","year":"2022","journal-title":"Nat. Commun."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"2078","DOI":"10.1002\/smll.201200168","article-title":"Chiral Pinwheel Clusters Lacking Local Point Chirality","volume":"8","author":"Sun","year":"2012","journal-title":"Small"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"1993","DOI":"10.1103\/PhysRevB.43.1993","article-title":"Efficient pseudopotentials for plane-wave calculations","volume":"43","author":"Troullier","year":"1991","journal-title":"Phys. Rev. B"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"17953","DOI":"10.1103\/PhysRevB.50.17953","article-title":"Projector augmented-wave method","volume":"50","year":"1994","journal-title":"Phys. Rev. B"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"3865","DOI":"10.1103\/PhysRevLett.77.3865","article-title":"Generalized gradient approximation made simple","volume":"77","author":"Perdew","year":"1996","journal-title":"Phys. Rev. Lett."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"154104","DOI":"10.1063\/1.3382344","article-title":"A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."}],"container-title":["Nanomaterials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-4991\/16\/7\/399\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,3,26]],"date-time":"2026-03-26T13:42:40Z","timestamp":1774532560000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-4991\/16\/7\/399"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,3,26]]},"references-count":42,"journal-issue":{"issue":"7","published-online":{"date-parts":[[2026,4]]}},"alternative-id":["nano16070399"],"URL":"https:\/\/doi.org\/10.3390\/nano16070399","relation":{},"ISSN":["2079-4991"],"issn-type":[{"value":"2079-4991","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,3,26]]}}}