{"paper_id":"299780fe-6ef0-468f-b356-24820a9f7e77","body_text":"Polymer Connectivity Governs Electrophotocatalytic Activity in the Solid State | 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 Polymer Connectivity Governs Electrophotocatalytic Activity in the Solid State Phillip Milner, Jianheng Ling, Amy Vonder Haar, Kiser Colley, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5428587/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 reductive functionalization of inert substrates like chloroarenes is a critical yet challenging transformation relevant to both environmental remediation and organic synthesis. Combining electricity and light is an emerging approach to access the deeply reducing potentials required for single electron transfer to chloroarenes, yet this approach is held back by the poor stability and mechanistic ambiguity of current homogeneous systems. Incorporating redox-active moieties into insoluble organic materials represents a promising strategy to unlock new heterogeneous catalytic activity while improving catalyst stability. Herein, we demonstrate the first example of heterogeneous electrophotocatalysis using redox-active rylene diimide polymers for the reduction of chloroarenes. In particular, we find that the electrophotocatalytic activity varies significantly not just as a function of the rylene diimide but also of the redox-inactive polymer backbone. In particular, PTCDA-en, a flexible, non-conjugated perylenediimide polymer, outperforms all other tested materials as an electrophotocatalyst. Using transient absorption spectroscopy, we reveal that precomplexation between the closed-shell PTCDA-en2− and the haloarene substrate is key to productive catalysis. Overall, our work represents the first example of heterogeneous electrophotocatalysis using an insoluble redox-active organic material and provides critical insights into how polymer structure dictates electrophotocatalytic activity in the solid state, guiding the development of next-generation heterogeneous (electro)photocatalysts for sustainable synthesis. Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology Physical sciences/Chemistry/Polymer chemistry Physical sciences/Chemistry/Photochemistry/Photocatalysis Physical sciences/Chemistry/Electrochemistry/Electrocatalysis Physical sciences/Chemistry/Physical chemistry/Excited states Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SupportingInformationFinal.docx 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. 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-5428587\",\"acceptedTermsAndConditions\":true,\"allowDirectSubmit\":false,\"archivedVersions\":[],\"articleType\":\"Article\",\"associatedPublications\":[],\"authors\":[{\"id\":382440376,\"identity\":\"b8130eb5-e5f0-48db-8f0b-3e5396763777\",\"order_by\":0,\"name\":\"Phillip 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