A framework for accessing elusive intermediate-sized PdnL2n (n = 8, 9) metal-organic cages

A framework for accessing elusive intermediate-sized PdnL2n (n = 8, 9) metal-organic cages | 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 A framework for accessing elusive intermediate-sized PdnL2n (n = 8, 9) metal-organic cages Ben Pilgrim, Connor Bergin, Daniel Murchie, Stephen Argent, Soumalya Bhattacharyya This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8405766/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 Within the extensive family of PdnL2n metal-organic cages (MOCs), some structures are much easier to access than others. Small structures (Pd2L4 to Pd6L12) and large pseudospherical structures (≥Pd12L24) can be readily obtained from flat aryl-based ligands. Intermediate-sized, lower-symmetry PdnL2n MOCs have remained challenging to access as thermodynamic products, limiting structural diversity. We present a general design strategy exploiting dihedral twisting and imidazole offset in bisimidazole-naphthalene ligands to achieve the required coordination angles for Pd8L16 (~105.1°) and Pd9L18 (~109.5°) assemblies. This approach delivers the first thermodynamically stable Pd9L18 tricapped trigonal prism and two rare Pd8L16 square antiprisms, expanding the accessible range of PdnL2n geometries. Crystallographic analysis, supported by a newly developed mathematical framework, rationalises these assemblies and provides predictive guidelines for future cage design. Our findings establish a generalisable route to intermediate-sized MOCs, bridging the gap between small and large structures and enabling systematic control over symmetry and topology. Physical sciences/Chemistry/Supramolecular chemistry/Self-assembly Physical sciences/Chemistry/Supramolecular chemistry/Molecular capsules Full Text Additional Declarations There is NO Competing Interest. Supplementary Files AngleCalcScriptFinal.txt Angle calculation script SupplementaryInformationFinal.pdf Supplementary 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. 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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-8405766","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":573568030,"identity":"380c5412-4923-49d3-847d-a70e0e7122f8","order_by":0,"name":"Ben 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Small structures (Pd2L4 to Pd6L12) and large pseudospherical structures (≥Pd12L24) can be readily obtained from flat aryl-based ligands. Intermediate-sized, lower-symmetry PdnL2n MOCs have remained challenging to access as thermodynamic products, limiting structural diversity. We present a general design strategy exploiting dihedral twisting and imidazole offset in bisimidazole-naphthalene ligands to achieve the required coordination angles for Pd8L16 (~105.1°) and Pd9L18 (~109.5°) assemblies. This approach delivers the first thermodynamically stable Pd9L18 tricapped trigonal prism and two rare Pd8L16 square antiprisms, expanding the accessible range of PdnL2n geometries. Crystallographic analysis, supported by a newly developed mathematical framework, rationalises these assemblies and provides predictive guidelines for future cage design. 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