{"title":"简便合成咪唑烷基苯酚支撑的双铜(II/II)配合物:以 MeOCO2- 的形式活化和固定大气中的二氧化碳,显示外源桥调制磁交换耦合","authors":"","doi":"10.1016/j.ica.2024.122298","DOIUrl":null,"url":null,"abstract":"<div><p>Two imidazolidine grafted Schiff bases H<sub>3</sub>L<sub>2</sub> and H<sub>3</sub>L<sub>3</sub> have been utilized to fasten the Cu<sub>2</sub> core in four new complexes [Cu<sub>2</sub>(<em>μ</em>-L<sub>2</sub>)(<em>μ</em>-O<sub>2</sub>CMe)]·H<sub>2</sub>O (<strong>1</strong>·H<sub>2</sub>O), [Cu<sub>2</sub>(<em>μ</em>-L<sub>2</sub>)(<em>μ</em>-O<sub>2</sub>COMe)]·H<sub>2</sub>O (<strong>2</strong>·H<sub>2</sub>O), [Cu<sub>2</sub>(<em>μ</em>-L<sub>2</sub>)(<em>μ</em>-NO<sub>3</sub>)]·H<sub>2</sub>O (<strong>3</strong>·H<sub>2</sub>O) and [Cu<sub>2</sub>L<sub>3</sub>(<em>μ</em>-OAc)]·5H<sub>2</sub>O (<strong>4</strong>·5H<sub>2</sub>O). Room temperature solution reaction of H<sub>3</sub>L<sub>2</sub> with Cu<sub>2</sub>(OAc)<sub>4</sub>·2H<sub>2</sub>O provided <strong>1</strong>·H<sub>2</sub>O in good yield. Follow-up reaction of <strong>1</strong>·H<sub>2</sub>O with Et<sub>4</sub>NOH in air replaces <em>μ</em>-O<sub>2</sub>CMe (acetato) bridge by MeOCO<sub>2</sub><sup>−</sup> (monomethyl carbonato) linker in <strong>2</strong>·H<sub>2</sub>O. Single crystal X-ray structure established the individual complexes and confirmed the fixation of atmospheric CO<sub>2</sub>. Variable temperature (2 to 300 K) magnetic susceptibility measurements recognized the antiferromagnetic exchange interactions between the adjacent copper(II) centers in complexes <strong>2</strong> and <strong>3</strong>. The amount of spin–spin interactions are found to be higher for ancillary NO<sub>3</sub><sup>−</sup> bridge (−284 <!--> <!-->cm<sup>−1</sup>) compared to the <em>in situ</em> transformed MeOCO<sub>2</sub><sup>−</sup> bridged (−1.64 <!--> <!-->cm<sup>−1</sup>).</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Facile synthesis of imidazolidinyl phenolate supported Dicopper(II/II) Complexes: Activation and fixation of atmospheric CO2 as MeOCO2− showing exogenous bridge modulating magnetic exchange coupling\",\"authors\":\"\",\"doi\":\"10.1016/j.ica.2024.122298\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Two imidazolidine grafted Schiff bases H<sub>3</sub>L<sub>2</sub> and H<sub>3</sub>L<sub>3</sub> have been utilized to fasten the Cu<sub>2</sub> core in four new complexes [Cu<sub>2</sub>(<em>μ</em>-L<sub>2</sub>)(<em>μ</em>-O<sub>2</sub>CMe)]·H<sub>2</sub>O (<strong>1</strong>·H<sub>2</sub>O), [Cu<sub>2</sub>(<em>μ</em>-L<sub>2</sub>)(<em>μ</em>-O<sub>2</sub>COMe)]·H<sub>2</sub>O (<strong>2</strong>·H<sub>2</sub>O), [Cu<sub>2</sub>(<em>μ</em>-L<sub>2</sub>)(<em>μ</em>-NO<sub>3</sub>)]·H<sub>2</sub>O (<strong>3</strong>·H<sub>2</sub>O) and [Cu<sub>2</sub>L<sub>3</sub>(<em>μ</em>-OAc)]·5H<sub>2</sub>O (<strong>4</strong>·5H<sub>2</sub>O). Room temperature solution reaction of H<sub>3</sub>L<sub>2</sub> with Cu<sub>2</sub>(OAc)<sub>4</sub>·2H<sub>2</sub>O provided <strong>1</strong>·H<sub>2</sub>O in good yield. Follow-up reaction of <strong>1</strong>·H<sub>2</sub>O with Et<sub>4</sub>NOH in air replaces <em>μ</em>-O<sub>2</sub>CMe (acetato) bridge by MeOCO<sub>2</sub><sup>−</sup> (monomethyl carbonato) linker in <strong>2</strong>·H<sub>2</sub>O. Single crystal X-ray structure established the individual complexes and confirmed the fixation of atmospheric CO<sub>2</sub>. Variable temperature (2 to 300 K) magnetic susceptibility measurements recognized the antiferromagnetic exchange interactions between the adjacent copper(II) centers in complexes <strong>2</strong> and <strong>3</strong>. The amount of spin–spin interactions are found to be higher for ancillary NO<sub>3</sub><sup>−</sup> bridge (−284 <!--> <!-->cm<sup>−1</sup>) compared to the <em>in situ</em> transformed MeOCO<sub>2</sub><sup>−</sup> bridged (−1.64 <!--> <!-->cm<sup>−1</sup>).</p></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-08-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S002016932400389X\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S002016932400389X","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Facile synthesis of imidazolidinyl phenolate supported Dicopper(II/II) Complexes: Activation and fixation of atmospheric CO2 as MeOCO2− showing exogenous bridge modulating magnetic exchange coupling
Two imidazolidine grafted Schiff bases H3L2 and H3L3 have been utilized to fasten the Cu2 core in four new complexes [Cu2(μ-L2)(μ-O2CMe)]·H2O (1·H2O), [Cu2(μ-L2)(μ-O2COMe)]·H2O (2·H2O), [Cu2(μ-L2)(μ-NO3)]·H2O (3·H2O) and [Cu2L3(μ-OAc)]·5H2O (4·5H2O). Room temperature solution reaction of H3L2 with Cu2(OAc)4·2H2O provided 1·H2O in good yield. Follow-up reaction of 1·H2O with Et4NOH in air replaces μ-O2CMe (acetato) bridge by MeOCO2− (monomethyl carbonato) linker in 2·H2O. Single crystal X-ray structure established the individual complexes and confirmed the fixation of atmospheric CO2. Variable temperature (2 to 300 K) magnetic susceptibility measurements recognized the antiferromagnetic exchange interactions between the adjacent copper(II) centers in complexes 2 and 3. The amount of spin–spin interactions are found to be higher for ancillary NO3− bridge (−284 cm−1) compared to the in situ transformed MeOCO2− bridged (−1.64 cm−1).
期刊介绍:
Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews.
Topics covered include:
• chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies;
• synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs);
• reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models;
• applications of inorganic compounds, metallodrugs and molecule-based materials.
Papers composed primarily of structural reports will typically not be considered for publication.