{"title":"通过单核铜(II)配合物的结构和电化学性质评估具有吡啶/喹啉/异喹啉结合位点的含氧五齿配体。","authors":"Yuji Mikata, Mizuho Uchida, Hinata Koike, Sunao Shoji, Yutaka Ohsedo, Yasushi Kawai and Takashi Matsuo","doi":"10.1039/D3DT02814C","DOIUrl":null,"url":null,"abstract":"<p >Eighteen mononuclear copper(<small>II</small>) complexes with oxygen-containing N4O1 pentadentate ligands were prepared. The ligand library consists of 2-aminoethanol derivatives ((Ar<small><sup>1</sup></small>CH<small><sub>2</sub></small>)(Ar<small><sup>2</sup></small>CH<small><sub>2</sub></small>)NCH<small><sub>2</sub></small>CH<small><sub>2</sub></small>OCH<small><sub>2</sub></small>Ar<small><sup>3</sup></small>) bearing three nitrogen-containing heteroaromatics (Ars) including pyridine, quinoline and isoquinoline <em>via</em> a methylene linker. Systematic replacements of pyridine binding sites with quinolines and isoquinolines reveal the general trends in the perturbation of bond distances and angles, the redox potential and the absorption maximum wavelength of the copper(<small>II</small>) complexes, depending on the position and number of (iso)quinoline heteroaromatics. The small effect on the redox potentials resulting from quinoline substitution at the Ar<small><sup>3</sup></small> position (near oxygen) of the ligand comes from the steric hindrance of the <em>peri</em> hydrogen atom in the quinoline moiety at this position, which removes the counter anion to enhance the coordination of quinoline nitrogen and ether oxygen atoms to the metal centre. In the absorption spectra of copper(<small>II</small>) complexes in the d–d transition region, the quinoline substitution at this site (Ar<small><sup>3</sup></small>) exhibits an opposite effect to those at the Ar<small><sup>1</sup></small> and Ar<small><sup>2</sup></small> sites. The electronic and steric contributions of the heteroaromatic binding sites to the ligand properties are comprehensively discussed.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 46","pages":" 17375-17388"},"PeriodicalIF":3.5000,"publicationDate":"2023-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Evaluation of oxygen-containing pentadentate ligands with pyridine/quinoline/isoquinoline binding sites via the structural and electrochemical properties of mononuclear copper(ii) complexes†\",\"authors\":\"Yuji Mikata, Mizuho Uchida, Hinata Koike, Sunao Shoji, Yutaka Ohsedo, Yasushi Kawai and Takashi Matsuo\",\"doi\":\"10.1039/D3DT02814C\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Eighteen mononuclear copper(<small>II</small>) complexes with oxygen-containing N4O1 pentadentate ligands were prepared. The ligand library consists of 2-aminoethanol derivatives ((Ar<small><sup>1</sup></small>CH<small><sub>2</sub></small>)(Ar<small><sup>2</sup></small>CH<small><sub>2</sub></small>)NCH<small><sub>2</sub></small>CH<small><sub>2</sub></small>OCH<small><sub>2</sub></small>Ar<small><sup>3</sup></small>) bearing three nitrogen-containing heteroaromatics (Ars) including pyridine, quinoline and isoquinoline <em>via</em> a methylene linker. Systematic replacements of pyridine binding sites with quinolines and isoquinolines reveal the general trends in the perturbation of bond distances and angles, the redox potential and the absorption maximum wavelength of the copper(<small>II</small>) complexes, depending on the position and number of (iso)quinoline heteroaromatics. The small effect on the redox potentials resulting from quinoline substitution at the Ar<small><sup>3</sup></small> position (near oxygen) of the ligand comes from the steric hindrance of the <em>peri</em> hydrogen atom in the quinoline moiety at this position, which removes the counter anion to enhance the coordination of quinoline nitrogen and ether oxygen atoms to the metal centre. In the absorption spectra of copper(<small>II</small>) complexes in the d–d transition region, the quinoline substitution at this site (Ar<small><sup>3</sup></small>) exhibits an opposite effect to those at the Ar<small><sup>1</sup></small> and Ar<small><sup>2</sup></small> sites. The electronic and steric contributions of the heteroaromatic binding sites to the ligand properties are comprehensively discussed.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 46\",\"pages\":\" 17375-17388\"},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2023-10-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2023/dt/d3dt02814c\",\"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":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2023/dt/d3dt02814c","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Evaluation of oxygen-containing pentadentate ligands with pyridine/quinoline/isoquinoline binding sites via the structural and electrochemical properties of mononuclear copper(ii) complexes†
Eighteen mononuclear copper(II) complexes with oxygen-containing N4O1 pentadentate ligands were prepared. The ligand library consists of 2-aminoethanol derivatives ((Ar1CH2)(Ar2CH2)NCH2CH2OCH2Ar3) bearing three nitrogen-containing heteroaromatics (Ars) including pyridine, quinoline and isoquinoline via a methylene linker. Systematic replacements of pyridine binding sites with quinolines and isoquinolines reveal the general trends in the perturbation of bond distances and angles, the redox potential and the absorption maximum wavelength of the copper(II) complexes, depending on the position and number of (iso)quinoline heteroaromatics. The small effect on the redox potentials resulting from quinoline substitution at the Ar3 position (near oxygen) of the ligand comes from the steric hindrance of the peri hydrogen atom in the quinoline moiety at this position, which removes the counter anion to enhance the coordination of quinoline nitrogen and ether oxygen atoms to the metal centre. In the absorption spectra of copper(II) complexes in the d–d transition region, the quinoline substitution at this site (Ar3) exhibits an opposite effect to those at the Ar1 and Ar2 sites. The electronic and steric contributions of the heteroaromatic binding sites to the ligand properties are comprehensively discussed.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.