{"doi":"10.1002/anie.202311790","title":"Ligand Modifications Produce Two‐Step Magnetic Switching in a Cobalt(dioxolene) Complex","abstract":"Abstract Mononuclear monodioxolene valence tautomeric (VT) cobalt complexes typically exist in their low spin (l.s.) Co III (cat 2− ) and high spin (h.s.) Co II (sq⋅ − ) forms (cat 2− =catecholato, and sq⋅ − =seminquinonato forms of 3,5−di− t Bu‐1,2‐dioxolene), which reversibly interconvert via temperature‐dependent intramolecular electron transfer. Typically, the remaining four coordination sites on cobalt are supported by a tetradentate ligand whose properties influence the temperature at which VT occurs. We report that replacing one chelating pyridyl arm of tris(2‐pyridylmethyl)amine (tpa) with a weaker field ortho ‐anisole moiety facilitates access to a third magnetic state, and examine a series of related complexes. Variable temperature crystallographic, magnetic, calorimetric, and spectroscopic studies support that this third state is consistent with l.s. Co II (sq⋅ − ). Thus, our ligand modifications not only provide access to the VT transition from l.s. Co III (cat 2− ) to l.s. Co II (sq⋅ − ), but at higher temperatures, the complex undergoes spin crossover from l.s. Co II (sq⋅ − ) to h.s. Co II (sq⋅ − ), representing the first example of two‐step magnetic switching in a mononuclear monodioxolene cobalt complex. We hypothesize that ligand dynamicity may facilitate access to the rarely observed l.s. Co II (sq⋅ − ) intermediate state, suggesting a new design criterion in the development of stimulus‐responsive multi‐state molecular switches.","journal":"Angewandte Chemie International Edition","year":2023,"id":336565,"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":19,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9545,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2023-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":378738,"name":"Toby J. Woods","orcid":"0000-0002-1737-811X","position":1,"is_corresponding":false},{"id":765769,"name":"Lisa Olshansky","orcid":"0000-0003-1076-9318","position":2,"is_corresponding":false},{"id":1067379,"name":"Khadanand KC","orcid":"0000-0002-1258-8636","position":0,"is_corresponding":true}],"reference_count":39,"raw_metadata":null,"created_at":"2026-07-19T01:10:21.947540Z","pmid":"37733206","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":[]}