{"paper_id":"02cce9b5-9b6e-480d-a7d8-18045ebfc16d","body_text":"Tying Molecular 85 and 51 Knots via Aza-Indolyl Motif | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Tying Molecular 8 5 and 5 1 Knots via Aza-Indolyl Motif Guo-Xin Jin, Yan Zou, Haitong Tang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9478474/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract The synthesis of molecular topology beyond conventional symmetric knots remains a formidable challenge. Here, we report the first synthesis of the molecular 8_5 knot—a low-symmetry, representative pretzel knot with eight crossing points—via coordination-driven self-assembly. This knot was assembled from eight 4-azaindolyl ligand strands (L) and eight binuclear metal blocks (E1-Rh). These components intertwine in three-dimensional space in an alternating up-and-down fashion, forming a closed loop featuring eight crossings. Successful construction of this elusive 8_5 knot relies on our newly developed 4-azaindolyl ligand strand, whose unique electronic and steric properties enable tunable topological organisation. Exploiting this ligand design, we further systematically synthesized two 5_1 torus knots in high yields by tuning the size of the binuclear metal motifs, thereby validating the platform's broad applicability. This study fills a key gap concerning low-symmetry eight-crossing molecular knots and establishes a versatile route to accessing diverse molecular topologies. Physical sciences/Chemistry/Coordination chemistry/Organometallic chemistry/Ligands Physical sciences/Chemistry/Supramolecular chemistry/Self-assembly Full Text Additional Declarations There is NO Competing Interest. Supplementary Files 1.cif Crystal cif Data for complex 1 2Ir.cif Crystal cif Data for complex 2-Ir 2Rh.cif Crystal cif Data for complex 2-Rh Supportinginformation.docx Supporting Information Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {\"props\":{\"pageProps\":{\"initialData\":{\"identity\":\"rs-9478474\",\"acceptedTermsAndConditions\":true,\"allowDirectSubmit\":false,\"archivedVersions\":[],\"articleType\":\"Article\",\"associatedPublications\":[],\"authors\":[{\"id\":630905929,\"identity\":\"2b772d94-7ed5-485f-b78c-6ee18d07836c\",\"order_by\":0,\"name\":\"Guo-Xin Jin\",\"email\":\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA1ElEQVRIiWNgGAWjYHCChAMMFXIMDAdAbDaitZwxJk0LAwNjGyla5CMSHh4unGeQ2Hf87AGGD2WHGfhnN+DXYnjmQMLhmdsMEmeeyUtgnHHuMIPEnQMEtLQ3JBzm3fYnccOBHANm3rbDDAYSCQS0NDMAtcwxSNxw/o0B819itMizg2xpAGq5AbSFkRgtBjxAv/AcMzCeeeONwcGec+k8EjcI2TIjJ/kzT42BbN/5HMMHP8qs5fhnELLlAA9CxQEg5sGvHmRLA/sBgopGwSgYBaNghAMA6exKaxpBeSYAAAAASUVORK5CYII=\",\"orcid\":\"https://orcid.org/0000-0002-7149-5413\",\"institution\":\"Fudan University\",\"correspondingAuthor\":true,\"prefix\":\"\",\"firstName\":\"Guo-Xin\",\"middleName\":\"\",\"lastName\":\"Jin\",\"suffix\":\"\"},{\"id\":630905930,\"identity\":\"4fea8011-a99e-416f-b2f5-2cf690f74a57\",\"order_by\":1,\"name\":\"Yan Zou\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Fudan University\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Yan\",\"middleName\":\"\",\"lastName\":\"Zou\",\"suffix\":\"\"},{\"id\":630905931,\"identity\":\"6b799645-8ae2-43fe-b0ae-2ee14cbabb1a\",\"order_by\":2,\"name\":\"Haitong Tang\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"Fudan University\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Haitong\",\"middleName\":\"\",\"lastName\":\"Tang\",\"suffix\":\"\"}],\"badges\":[],\"createdAt\":\"2026-04-21 04:10:56\",\"currentVersionCode\":1,\"declarations\":\"\",\"doi\":\"10.21203/rs.3.rs-9478474/v1\",\"doiUrl\":\"https://doi.org/10.21203/rs.3.rs-9478474/v1\",\"draftVersion\":[],\"editorialEvents\":[],\"editorialNote\":\"\",\"failedWorkflow\":false,\"files\":[{\"id\":108183489,\"identity\":\"644a71f9-895a-4060-a0d3-56889e7c5c1d\",\"added_by\":\"auto\",\"created_at\":\"2026-04-30 09:01:39\",\"extension\":\"pdf\",\"order_by\":1,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"manuscript-pdf\",\"size\":774451,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"Manuscript.pdf\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-9478474/v1_covered_a2b57efa-f37b-49ef-95a4-e2a388bcafc1.pdf\"},{\"id\":108090319,\"identity\":\"5c336cff-0d61-4ff6-b9e8-74e56d432167\",\"added_by\":\"auto\",\"created_at\":\"2026-04-29 09:13:03\",\"extension\":\"cif\",\"order_by\":1,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":24266482,\"visible\":true,\"origin\":\"\",\"legend\":\"Crystal cif Data for complex 1\",\"description\":\"\",\"filename\":\"1.cif\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-9478474/v1/466ac9831843bf1f50a06315.cif\"},{\"id\":108090321,\"identity\":\"7d20ed29-68d1-407c-88c8-80752b21eafd\",\"added_by\":\"auto\",\"created_at\":\"2026-04-29 09:13:03\",\"extension\":\"cif\",\"order_by\":2,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":3997300,\"visible\":true,\"origin\":\"\",\"legend\":\"Crystal cif Data for complex 2-Ir\",\"description\":\"\",\"filename\":\"2Ir.cif\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-9478474/v1/c4524a7c5c84388c7b9e3606.cif\"},{\"id\":108181912,\"identity\":\"3f374d37-1f1c-4aff-a871-7043b95f4acf\",\"added_by\":\"auto\",\"created_at\":\"2026-04-30 08:59:00\",\"extension\":\"cif\",\"order_by\":3,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":9616802,\"visible\":true,\"origin\":\"\",\"legend\":\"Crystal cif Data for complex 2-Rh\",\"description\":\"\",\"filename\":\"2Rh.cif\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-9478474/v1/3c3c8522962c079b00539b55.cif\"},{\"id\":108090323,\"identity\":\"6b327a41-4c2b-402f-a834-8991b914b9a2\",\"added_by\":\"auto\",\"created_at\":\"2026-04-29 09:13:03\",\"extension\":\"docx\",\"order_by\":4,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":13193550,\"visible\":true,\"origin\":\"\",\"legend\":\"Supporting Information\",\"description\":\"\",\"filename\":\"Supportinginformation.docx\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-9478474/v1/f689d37fbf526157db627951.docx\"}],\"financialInterests\":\"There is \\u003cb\\u003eNO\\u003c/b\\u003e Competing Interest.\",\"formattedTitle\":\"\\u003cp\\u003e\\u003cstrong\\u003eTying Molecular 8\\u003c/strong\\u003e\\u003csub\\u003e\\u003cstrong\\u003e5\\u003c/strong\\u003e\\u003c/sub\\u003e\\u003cstrong\\u003e and 5\\u003c/strong\\u003e\\u003csub\\u003e\\u003cstrong\\u003e1\\u003c/strong\\u003e\\u003c/sub\\u003e\\u003cstrong\\u003e Knots via Aza-Indolyl Motif\\u003c/strong\\u003e\\u003c/p\\u003e\",\"fulltext\":[],\"fulltextSource\":\"\",\"fullText\":\"\",\"funders\":[],\"hasAdminPriorityOnWorkflow\":false,\"hasManuscriptDocX\":false,\"hasOptedInToPreprint\":true,\"hasPassedJournalQc\":\"\",\"hasAnyPriority\":true,\"hideJournal\":false,\"highlight\":\"\",\"institution\":\"\",\"isAcceptedByJournal\":false,\"isAuthorSuppliedPdf\":true,\"isDeskRejected\":\"\",\"isHiddenFromSearch\":false,\"isInQc\":false,\"isInWorkflow\":false,\"isPdf\":true,\"isPdfUpToDate\":true,\"isWithdrawnOrRetracted\":false,\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"nature-portfolio\",\"isNatureJournal\":true,\"hasQc\":false,\"allowDirectSubmit\":false,\"externalIdentity\":\"\",\"sideBox\":\"\",\"snPcode\":\"\",\"submissionUrl\":\"\",\"title\":\"Nature Portfolio\",\"twitterHandle\":\"\",\"acdcEnabled\":false,\"dfaEnabled\":false,\"editorialSystem\":\"ejp\",\"reportingPortfolio\":\"\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false},\"keywords\":\"\",\"lastPublishedDoi\":\"10.21203/rs.3.rs-9478474/v1\",\"lastPublishedDoiUrl\":\"https://doi.org/10.21203/rs.3.rs-9478474/v1\",\"license\":{\"name\":\"CC BY 4.0\",\"url\":\"https://creativecommons.org/licenses/by/4.0/\"},\"manuscriptAbstract\":\"The synthesis of molecular topology beyond conventional symmetric knots remains a formidable challenge. Here, we report the first synthesis of the molecular 8_5 knot—a low-symmetry, representative pretzel knot with eight crossing points—via coordination-driven self-assembly. This knot was assembled from eight 4-azaindolyl ligand strands (L) and eight binuclear metal blocks (E1-Rh). These components intertwine in three-dimensional space in an alternating up-and-down fashion, forming a closed loop featuring eight crossings. Successful construction of this elusive 8_5 knot relies on our newly developed 4-azaindolyl ligand strand, whose unique electronic and steric properties enable tunable topological organisation. Exploiting this ligand design, we further systematically synthesized two 5_1 torus knots in high yields by tuning the size of the binuclear metal motifs, thereby validating the platform's broad applicability. This study fills a key gap concerning low-symmetry eight-crossing molecular knots and establishes a versatile route to accessing diverse molecular topologies.\",\"manuscriptTitle\":\"Tying Molecular 85 and 51 Knots via Aza-Indolyl Motif\",\"msid\":\"\",\"msnumber\":\"\",\"nonDraftVersions\":[{\"code\":1,\"date\":\"2026-04-29 09:12:59\",\"doi\":\"10.21203/rs.3.rs-9478474/v1\",\"editorialEvents\":[],\"status\":\"published\",\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"nature-synthesis\",\"isNatureJournal\":true,\"hasQc\":false,\"allowDirectSubmit\":false,\"externalIdentity\":\"natsynth\",\"sideBox\":\"Learn more about [Nature Synthesis](https://www.nature.com/natsynth/)\",\"snPcode\":\"\",\"submissionUrl\":\"https://mts-natsynth.nature.com/cgi-bin/main.plex\",\"title\":\"Nature Synthesis\",\"twitterHandle\":\"\",\"acdcEnabled\":true,\"dfaEnabled\":true,\"editorialSystem\":\"ejp\",\"reportingPortfolio\":\"Nature Research\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false}}],\"origin\":\"\",\"ownerIdentity\":\"ec68a285-0392-452c-8ccb-cc935cbc06d3\",\"owner\":[],\"postedDate\":\"April 29th, 2026\",\"published\":true,\"recentEditorialEvents\":[{\"type\":\"reviewerAgreed\",\"content\":\"This content is not available.\",\"date\":\"2026-05-08T12:41:09+00:00\",\"index\":4,\"fulltext\":\"This content is not available.\"},{\"type\":\"reviewerAgreed\",\"content\":\"This content is not available.\",\"date\":\"2026-05-07T13:19:30+00:00\",\"index\":3,\"fulltext\":\"This content is not available.\"},{\"type\":\"reviewerAgreed\",\"content\":\"This content is not available.\",\"date\":\"2026-05-07T05:43:05+00:00\",\"index\":2,\"fulltext\":\"This content is not available.\"}],\"rejectedJournal\":[],\"revision\":\"\",\"amendment\":\"\",\"status\":\"under-review\",\"subjectAreas\":[{\"id\":67229660,\"name\":\"Physical sciences/Chemistry/Coordination chemistry/Organometallic chemistry/Ligands\"},{\"id\":67229661,\"name\":\"Physical sciences/Chemistry/Supramolecular chemistry/Self-assembly\"}],\"tags\":[],\"updatedAt\":\"2026-04-29T09:12:59+00:00\",\"versionOfRecord\":[],\"versionCreatedAt\":\"2026-04-29 09:12:59\",\"video\":\"\",\"vorDoi\":\"\",\"vorDoiUrl\":\"\",\"workflowStages\":[]},\"version\":\"v1\",\"identity\":\"rs-9478474\",\"journalConfig\":\"researchsquare\"},\"__N_SSP\":true},\"page\":\"/article/[identity]/[[...version]]\",\"query\":{\"redirect\":\"/article/rs-9478474\",\"identity\":\"rs-9478474\",\"version\":[\"v1\"]},\"buildId\":\"XKTyCvWXoU3ODBz1xrDgd\",\"isFallback\":false,\"isExperimentalCompile\":false,\"dynamicIds\":[84888],\"gssp\":true,\"scriptLoader\":[]}","source_license":"CC-BY-4.0","license_restricted":false}