64414 2025 eng 1 6 49 64 article Wiley VHC-Verlag 1 -- -- -- AbstractWe report the synthesis of a planarized tris‐amidobismuthane supported by a rigid, bulky NNN pincer ligand, which enforces a T‐shaped geometry at the bismuth center. The Bi(NNN) complex features a low‐lying LUMO with distinct Bi(6p) orbital character as shown by DFT calculations. Cyclic voltammetry reveals a fully reversible one‐electron reduction at E1/2 = –1.85 V versus Fc0/+ in THF. Chemical reduction with KC8 in the presence of 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane (222‐crypt) enables the isolation of an unprecedented Bi(II) radical anion in high isolated yields. Multi‐frequency EPR, X‐ray absorption spectroscopy and SQUID magnetometry complemented by theoretical calculations confirm localization of the unpaired electron on the bismuth center. Preliminary reactivity studies display radical reactivity as shown by single‐electron transfer chemistry and radical coupling reactions. Angewandte Chemie International Edition 1433-7851 10.1002/anie.202515545 urn:nbn:de:kobv:b43-644143 true journal-article http://creativecommons.org/licenses/by/4.0/ crossref PersonAuthorFirstName_1,PersonAuthorLastName_1,PersonAuthorIdentifierOrcid_1,PersonAuthorFirstName_2,PersonAuthorLastName_2,PersonAuthorIdentifierOrcid_2,PersonAuthorFirstName_3,PersonAuthorLastName_3,PersonAuthorIdentifierOrcid_3,PersonAuthorFirstName_4,PersonAuthorLastName_4,PersonAuthorIdentifierOrcid_4,PersonAuthorFirstName_5,PersonAuthorLastName_5,PersonAuthorIdentifierOrcid_5,PersonAuthorFirstName_6,PersonAuthorLastName_6,PersonAuthorIdentifierOrcid_6,PersonAuthorFirstName_7,PersonAuthorLastName_7,PersonAuthorIdentifierOrcid_7,PublisherName,TitleMain_1,Language,TitleAbstract_1,TitleParent_1,ArticleNumber,PublishedYear,IdentifierIssn,Enrichmentlocal_crossrefLicence doi-import 20.10.2025 Creative Commons - CC BY - Namensnennung 4.0 International Sotirios Pavlidis Christian Teutloff Ana de Oliveira Guilherme Buzanich Konstantin B. Krause Franziska Emmerling Robert Bittl Josh Abbenseth eng uncontrolled Bi(III) Ingenieurwissenschaften und zugeordnete Tätigkeiten 6 Materialchemie 6.3 Strukturanalytik Material Verlagsliteratur Datei für die Öffentlichkeit verfügbar ("Open Access") Wissenschaftliche Artikel der BAM 6.0 Abteilungsleitung und andere Advanced Materials Bundesanstalt für Materialforschung und -prüfung (BAM) https://opus4.kobv.de/opus4-bam/files/64414/Angewandte.pdf