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However, this approach is seldom utilized to develop materials that exhibit stimuli\u2010responsive circularly polarized luminescence (CPL). Herein, we present the synthesis and characterization of enantiomeric hybrid zinc bromides: biprotonated ((<jats:italic>R\/S<\/jats:italic>)\u2010C<jats:sub>12<\/jats:sub>H<jats:sub>16<\/jats:sub>N<jats:sub>2<\/jats:sub>)ZnBr<jats:sub>4<\/jats:sub> ((<jats:italic>R\/S<\/jats:italic>\u2010LH2)ZnBr<jats:sub>4<\/jats:sub>) and monoprotonated ((<jats:italic>R\/S<\/jats:italic>)\u2010C<jats:sub>12<\/jats:sub>H<jats:sub>15<\/jats:sub>N<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>ZnBr<jats:sub>4<\/jats:sub> ((<jats:italic>R\/S<\/jats:italic>\u2010LH1)<jats:sub>2<\/jats:sub>ZnBr<jats:sub>4<\/jats:sub>), derived from the chiral organic amine (<jats:italic>R\/S<\/jats:italic>)\u20102,3,4,9\u2010Tetrahydro\u20101H\u2010carbazol\u20103\u2010amine ((<jats:italic>R\/S<\/jats:italic>)\u2010C<jats:sub>12<\/jats:sub>H<jats:sub>14<\/jats:sub>N<jats:sub>2<\/jats:sub>). These compounds showcase luminescent properties; the zero\u2010dimensional biprotonated form emits green light at 505\u2005nm, while the monoprotonated form, with a pseudo\u2010layered structure, displays red luminescence at 599 and 649\u2005nm. Remarkably, the reversible local protonation\u2010deprotonation behavior of the organic cations allows for exposure to polar solvents and heating to induce reversible structural and luminescent transformations between the two forms. Theoretical calculations reveal that the lower energy barrier associated with the deprotonation process within the pyrrole ring is responsible for the local protonation\u2010deprotonation behavior observed. These enantiomorphic hybrid zinc bromides also exhibit switchable circular dichroism (CD) and CPL properties. Furthermore, their chloride counterparts were successfully obtained by adjusting the halogen ions. Importantly, the unique stimuli\u2010responsive CPL characteristics position these hybrid zinc halides as promising candidates for applications in information storage, anti\u2010counterfeiting, and information encryption.<\/jats:p>","DOI":"10.1002\/anie.202410416","type":"journal-article","created":{"date-parts":[[2024,8,13]],"date-time":"2024-08-13T02:14:11Z","timestamp":1723515251000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":49,"title":["Reversible Local Protonation\u2010Deprotonation: Tuning Stimuli\u2010Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti\u2010Counterfeiting and Encryption"],"prefix":"10.1002","volume":"63","author":[{"given":"Dan\u2010Yang","family":"Liu","sequence":"first","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials Henan International Joint Laboratory of Tumor Theranostical Cluster Materials Green Catalysis Center, and College of Chemistry Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lin\u2010Yuan","family":"Xiong","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials Henan International Joint Laboratory of Tumor Theranostical Cluster Materials Green Catalysis Center, and College of Chemistry Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xi\u2010Yan","family":"Dong","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials Henan International Joint Laboratory of Tumor Theranostical Cluster Materials Green Catalysis Center, and College of Chemistry Zhengzhou University  Zhengzhou 450001 China"},{"name":"College of Chemistry and Chemical Engineering Henan Polytechnic University  Jiaozuo 454000 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhen","family":"Han","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials Henan International Joint Laboratory of Tumor Theranostical Cluster Materials Green Catalysis Center, and College of Chemistry Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hua\u2010Li","family":"Liu","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials Henan International Joint Laboratory of Tumor Theranostical Cluster Materials Green Catalysis Center, and College of Chemistry Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6728-0559","authenticated-orcid":false,"given":"Shuang\u2010Quan","family":"Zang","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials Henan International Joint Laboratory of Tumor Theranostical Cluster Materials Green Catalysis Center, and College of Chemistry Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,10,8]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/adom.202202811"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c05080"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.0c02729"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c09395"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c01214"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202109595"},{"key":"e_1_2_7_7_1","unstructured":"\u00a0"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202313590"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c03322"},{"key":"e_1_2_7_10_1","unstructured":"\u00a0"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.202110771"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.202109277"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/adom.202101700"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201702825"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.202309296"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202206437"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202200609"},{"key":"e_1_2_7_18_1","unstructured":"\u00a0"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/agt2.141"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00191K"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/agt2.48"},{"key":"e_1_2_7_22_1","unstructured":"\u00a0"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202307875"},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202212685"},{"key":"e_1_2_7_25_1","unstructured":"\u00a0"},{"key":"e_1_2_7_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202008004"},{"key":"e_1_2_7_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c09454"},{"key":"e_1_2_7_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b02365"},{"key":"e_1_2_7_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/adom.202301864"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202211808"},{"key":"e_1_2_7_31_1","unstructured":"\u00a0"},{"key":"e_1_2_7_32_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cclet.2022.107980"},{"key":"e_1_2_7_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c05063"},{"key":"e_1_2_7_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202309906"},{"key":"e_1_2_7_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/smll.202300938"},{"key":"e_1_2_7_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.1c01134"},{"key":"e_1_2_7_37_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202306821"},{"key":"e_1_2_7_38_1","unstructured":"\u00a0"},{"key":"e_1_2_7_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/adom.202301843"},{"key":"e_1_2_7_40_2","doi-asserted-by":"publisher","DOI":"10.1039\/D3CC01461D"},{"key":"e_1_2_7_41_1","unstructured":"\u00a0"},{"key":"e_1_2_7_42_2","doi-asserted-by":"publisher","DOI":"10.1002\/adom.202200386"},{"key":"e_1_2_7_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/acsomega.8b02883"},{"key":"e_1_2_7_44_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.9b00537"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c08794"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.3c00784"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201710383"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c04832"},{"key":"e_1_2_7_49_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202205906"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-023-38927-2"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1002\/agt2.311"},{"key":"e_1_2_7_52_1","unstructured":"Deposition 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