{"doi":"10.1021/acsapm.2c02047","title":"Unexpected Direct Synthesis of Tunable Redox-Active Benzil-Linked Polymers via the Benzoin Reaction","abstract":"Strategies for the sustainable synthesis of redox-active organic polymers could lead to next-generation organic electrode materials for electrochemical energy storage, electrocatalysis, and electro-swing chemical separations. Among redox-active moieties, benzils or aromatic 1,2-diones are particularly attractive due to their high theoretical gravimetric capacities and fast charge/discharge rates. Herein, we demonstrate that the cyanide-catalyzed polymerization of simple dialdehyde monomers unexpectedly leads to insoluble redox-active benzil-linked polymers instead of the expected benzoin polymers, as supported by solid-state nuclear magnetic resonance spectroscopy and electrochemical characterization. Mechanistic studies suggest that cyanide-mediated benzoin oxidation occurs by hydride transfer to the solvent and that the insolubility of the benzil-linked polymers protects them from subsequent cyanolysis. The thiophene-based polymer poly(BTDA) is an intriguing organic electrode material that demonstrates two reversible one-electron reductions with monovalent cations such as Li+ and Na+ but one two-electron reduction with divalent Mg2+. As such, the tandem benzoin-oxidation polymerization reported herein represents a sustainable method for the synthesis of highly tunable and redox-active organic materials.","journal":"ACS Applied Polymer Materials","year":2022,"id":291729,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":3,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9503,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2022-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":663538,"name":"Jaehwan Kim","orcid":"0000-0003-1311-4982","position":1,"is_corresponding":false},{"id":545523,"name":"Cara N. Gannett","orcid":"0000-0002-2383-6244","position":2,"is_corresponding":false},{"id":545525,"name":"Héctor D. Abruña","orcid":"0000-0002-3948-356X","position":3,"is_corresponding":false},{"id":228304,"name":"Phillip J. Milner","orcid":"0000-0002-2618-013X","position":4,"is_corresponding":false},{"id":975449,"name":"Christina Cong","orcid":null,"position":0,"is_corresponding":true}],"reference_count":70,"raw_metadata":null,"created_at":"2026-07-19T00:30:38.420009Z","pmid":"37123564","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}