{"doi":"10.1021/acs.macromol.0c02245","title":"Solvent Effects and Side Reactions in Organocatalyzed Atom Transfer Radical Polymerization for Enabling the Controlled Polymerization of Acrylates Catalyzed by Diaryl Dihydrophenazines","abstract":"Investigation of the effects of a solvent on the photophysical and redox properties of the photoredox catalyst (PC), N,N-di(2-naphthyl)-5,10-dihydrophenazine (PC 1), revealed the opportunity to use tetrahydrofuran (THF) to modulate the reactivity of PC 1 toward achieving a controlled organocatalyzed atom transfer radial polymerization (O-ATRP) of acrylates. Compared with dimethylacetamide (DMAc), in tetrahydrofuran (THF), PC 1 exhibits a higher quantum yield of intersystem crossing (ΦISC = 0.02 in DMAc, 0.30 in THF), a longer singlet excited-state lifetime (τSinglet = 3.81 ns in DMAc, 21.5 ns in THF), and a longer triplet excited-state lifetime (τTriplet = 4.3 μs in DMAc, 15.2 μs in THF). Destabilization of 1•+, the proposed polymerization deactivator, in THF leads to an increase in the oxidation potential of this species by 120 mV (E1/20 = 0.22 V vs SCE in DMAc, 0.34 V vs SCE in THF). The O-ATRP of n-butyl acrylate (n-BA) catalyzed by PC 1 proceeds in a more controlled fashion in THF than in DMAc, producing P(n-BA) with low dispersity, Đ (Đ < 1.2). Model reactions and spectroscopic experiments revealed that two initiator-derived alkyl radicals add to the core of PC 1 to form an alkyl-substituted photocatalyst (2) during the polymerization. PC 2 accesses a polar CT excited state that is ∼40 meV higher in energy than PC 1 and forms a slightly more oxidizing radical cation (E1/20 = 0.22 V for 1•+ and 0.25 V for 2•+ in DMAc). A new O-ATRP procedure was developed wherein PC 1 is converted to 2 in situ. The application of this method enabled the O-ATRP of a number of acrylates to proceed with moderate to good control (Đ = 1.15–1.45 and I* = 83–127%).","journal":"Macromolecules","year":2020,"id":93949,"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":39,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9477,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2020-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":468852,"name":"Steven M. Sartor","orcid":null,"position":1,"is_corresponding":false},{"id":468347,"name":"Justin P. Cole","orcid":"0000-0001-7698-4550","position":2,"is_corresponding":false},{"id":468348,"name":"Niels H. Damrauer","orcid":"0000-0001-8337-9375","position":3,"is_corresponding":false},{"id":274820,"name":"Garret M. Miyake","orcid":"0000-0003-2451-7090","position":4,"is_corresponding":false},{"id":468346,"name":"Blaine G. McCarthy","orcid":"0000-0003-3816-6455","position":0,"is_corresponding":true}],"reference_count":56,"raw_metadata":null,"created_at":"2026-07-18T22:31:34.149524Z","pmid":"34267405","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":[]}