Large Stimuli-Responsive Azobenzene Macrocycles as Functional Cavitands: Synthesis and Detection by NMR and MS Methods

Large Stimuli-Responsive Azobenzene Macrocycles as Functional Cavitands: Synthesis and Detection by NMR and MS Methods | 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 Large Stimuli-Responsive Azobenzene Macrocycles as Functional Cavitands: Synthesis and Detection by NMR and MS Methods Helena Roithmeyer, Merle Uudsemaa, Aleksander Trummal, Mari-Liis Brük, and 8 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-2621025/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 Azobenzene macrocycles are widely investigated as potential drug delivery systems and as part of molecular machines due to their photo-responsive properties. Herein, we synthesize a series of new azobenzene macrocycles, featuring up to eight switchable repeating units. We study the influence of different reaction conditions, base equivalents, concentration, reactant addition time and stirring time, on the formation of the macrocycles of different sizes, ranging from 10 to 40 aromatic rings in the macrocyclic architectures. High-resolution mass spectrometry and ion mobility (IM) mass spectrometry experiments and 1 H and diffusion-ordered spectroscopy (DOSY) NMR are used to detect the presence of the macrocycles in gas phase and solution, respectively. While MS methods lead to the identification of the macrocycles, the differentiation between the different sizes of these macrocycles with DOSY NMR is limited. The responsiveness of the Z-to-E photo-switching of the smallest of the macrocycles, exhibiting 2 azobenzene units and in total 10 aromatic rings, separated with column chromatography, is studied with irradiation experiments, using both UV-Vis light and thermal excitation, and monitoring the sample with UV-Vis absorption and 1 H NMR spectroscopy after the excitation. DFT calculations help shed light on the conformation of this isolated species. Physical sciences/Chemistry/Supramolecular chemistry/Molecular capsules Physical sciences/Chemistry/Analytical chemistry/Mass spectrometry Physical sciences/Chemistry/Analytical chemistry/NMR spectroscopy/Solution-state NMR Full Text Additional Declarations There is NO Competing Interest. Supplementary Files AzobenzenemacrocyclesmanuscriptSI.pdf 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-2621025","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":179934453,"identity":"b1137dde-576e-41ba-b1cd-ad12e9467a3a","order_by":0,"name":"Helena Roithmeyer","email":"","orcid":"https://orcid.org/0000-0002-6585-5953","institution":"University of Zurich","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Helena","middleName":"","lastName":"Roithmeyer","suffix":""},{"id":179934454,"identity":"aa2bbb5b-84d4-4de8-ae33-ed2e7204db4e","order_by":1,"name":"Merle 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Herein, we synthesize a series of new azobenzene macrocycles, featuring up to eight switchable repeating units. We study the influence of different reaction conditions, base equivalents, concentration, reactant addition time and stirring time, on the formation of the macrocycles of different sizes, ranging from 10 to 40 aromatic rings in the macrocyclic architectures. High-resolution mass spectrometry and ion mobility (IM) mass spectrometry experiments and \u003csup\u003e1\u003c/sup\u003eH and diffusion-ordered spectroscopy (DOSY) NMR are used to detect the presence of the macrocycles in gas phase and solution, respectively. While MS methods lead to the identification of the macrocycles, the differentiation between the different sizes of these macrocycles with DOSY NMR is limited. 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