Xiaodi Du, Zhiqiang Zhang, Congli Gao, Fengcai Li and Xi-Li Li
{"title":"两对手性YbII对映体具有不同的近红外发光和圆偏振发光性能,二次谐波产生响应存在巨大差异","authors":"Xiaodi Du, Zhiqiang Zhang, Congli Gao, Fengcai Li and Xi-Li Li","doi":"10.1039/D3DT03324D","DOIUrl":null,"url":null,"abstract":"<p >By introducing enantiomerically pure mono-bidentate N-donor ligands (L<small><sub><em>R</em></sub></small>/L<small><sub><em>S</em></sub></small>) into Yb(btfa)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small> and Yb(dbm)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O), respectively, two pairs of chiral Yb<small><sup>III</sup></small> enantiomers, namely Yb(btfa)<small><sub>3</sub></small>L<small><sub><em>R</em></sub></small>/Yb(btfa)<small><sub>3</sub></small>L<small><sub><em>S</em></sub></small> (<strong>D-1/L-1</strong>) and [Yb(dbm)<small><sub>3</sub></small>L<small><sub><em>R</em></sub></small>]·[Yb(dbm)<small><sub>3</sub></small>(C<small><sub>2</sub></small>H<small><sub>5</sub></small>OH)]/[Yb(dbm)<small><sub>3</sub></small>L<small><sub><em>S</em></sub></small>]·[Yb(dbm)<small><sub>3</sub></small>(C<small><sub>2</sub></small>H<small><sub>5</sub></small>OH)] (<strong>D-2/L-2</strong>) were isolated, where btfa<small><sup>−</sup></small> = 3-benzoyl-1,1,1-trifluoroacetonate, dbm<small><sup>−</sup></small> = dibenzoylmethanate, and L<small><sub><em>R</em></sub></small>/L<small><sub><em>S</em></sub></small> = (−)/(+)-4,5-pinenepyridyl-2-pyrazine. <strong>D-1/L-1</strong> possess mononuclear structures in which the Yb<small><sup>III</sup></small> ions are eight-coordinated, while <strong>D-2/L-2</strong> show cocrystal structures containing Yb(dbm)<small><sub>3</sub></small>(L<small><sub><em>R</em></sub></small>/L<small><sub><em>S</em></sub></small>) and Yb(dbm)<small><sub>3</sub></small>(C<small><sub>2</sub></small>H<small><sub>5</sub></small>OH) moieties in which the two Yb<small><sup>III</sup></small> ions are eight and seven-coordinated, respectively. They not only feature different molecular structures but also present distinct linear and nonlinear optical performances. Chiral mononuclear <strong>D-1</strong> has better near infrared photo-luminescence (NIR-PL) and circularly polarized luminescence (CPL) performances than chiral cocrystal <strong>D-2</strong>. More remarkably, <strong>D-1/L-1</strong> show large second-harmonic generation (SHG) responses (up to 1.25/1.28 × KDP) 18/16 times those of <strong>D-2/L-2</strong> (0.07/0.08 × KDP). In addition, <strong>D-2/L-2</strong> represent the first examples of lanthanide cocrystal complexes with NIR-PL, NIR-CPL and SHG properties.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 47","pages":" 17758-17766"},"PeriodicalIF":3.5000,"publicationDate":"2023-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Two pairs of chiral YbIII enantiomers presenting distinct NIR luminescence and circularly polarized luminescence performances with giant differences in second-harmonic generation responses†\",\"authors\":\"Xiaodi Du, Zhiqiang Zhang, Congli Gao, Fengcai Li and Xi-Li Li\",\"doi\":\"10.1039/D3DT03324D\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >By introducing enantiomerically pure mono-bidentate N-donor ligands (L<small><sub><em>R</em></sub></small>/L<small><sub><em>S</em></sub></small>) into Yb(btfa)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small> and Yb(dbm)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O), respectively, two pairs of chiral Yb<small><sup>III</sup></small> enantiomers, namely Yb(btfa)<small><sub>3</sub></small>L<small><sub><em>R</em></sub></small>/Yb(btfa)<small><sub>3</sub></small>L<small><sub><em>S</em></sub></small> (<strong>D-1/L-1</strong>) and [Yb(dbm)<small><sub>3</sub></small>L<small><sub><em>R</em></sub></small>]·[Yb(dbm)<small><sub>3</sub></small>(C<small><sub>2</sub></small>H<small><sub>5</sub></small>OH)]/[Yb(dbm)<small><sub>3</sub></small>L<small><sub><em>S</em></sub></small>]·[Yb(dbm)<small><sub>3</sub></small>(C<small><sub>2</sub></small>H<small><sub>5</sub></small>OH)] (<strong>D-2/L-2</strong>) were isolated, where btfa<small><sup>−</sup></small> = 3-benzoyl-1,1,1-trifluoroacetonate, dbm<small><sup>−</sup></small> = dibenzoylmethanate, and L<small><sub><em>R</em></sub></small>/L<small><sub><em>S</em></sub></small> = (−)/(+)-4,5-pinenepyridyl-2-pyrazine. <strong>D-1/L-1</strong> possess mononuclear structures in which the Yb<small><sup>III</sup></small> ions are eight-coordinated, while <strong>D-2/L-2</strong> show cocrystal structures containing Yb(dbm)<small><sub>3</sub></small>(L<small><sub><em>R</em></sub></small>/L<small><sub><em>S</em></sub></small>) and Yb(dbm)<small><sub>3</sub></small>(C<small><sub>2</sub></small>H<small><sub>5</sub></small>OH) moieties in which the two Yb<small><sup>III</sup></small> ions are eight and seven-coordinated, respectively. They not only feature different molecular structures but also present distinct linear and nonlinear optical performances. Chiral mononuclear <strong>D-1</strong> has better near infrared photo-luminescence (NIR-PL) and circularly polarized luminescence (CPL) performances than chiral cocrystal <strong>D-2</strong>. More remarkably, <strong>D-1/L-1</strong> show large second-harmonic generation (SHG) responses (up to 1.25/1.28 × KDP) 18/16 times those of <strong>D-2/L-2</strong> (0.07/0.08 × KDP). In addition, <strong>D-2/L-2</strong> represent the first examples of lanthanide cocrystal complexes with NIR-PL, NIR-CPL and SHG properties.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 47\",\"pages\":\" 17758-17766\"},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2023-11-09\",\"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/d3dt03324d\",\"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/d3dt03324d","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Two pairs of chiral YbIII enantiomers presenting distinct NIR luminescence and circularly polarized luminescence performances with giant differences in second-harmonic generation responses†
By introducing enantiomerically pure mono-bidentate N-donor ligands (LR/LS) into Yb(btfa)3(H2O)2 and Yb(dbm)3(H2O), respectively, two pairs of chiral YbIII enantiomers, namely Yb(btfa)3LR/Yb(btfa)3LS (D-1/L-1) and [Yb(dbm)3LR]·[Yb(dbm)3(C2H5OH)]/[Yb(dbm)3LS]·[Yb(dbm)3(C2H5OH)] (D-2/L-2) were isolated, where btfa− = 3-benzoyl-1,1,1-trifluoroacetonate, dbm− = dibenzoylmethanate, and LR/LS = (−)/(+)-4,5-pinenepyridyl-2-pyrazine. D-1/L-1 possess mononuclear structures in which the YbIII ions are eight-coordinated, while D-2/L-2 show cocrystal structures containing Yb(dbm)3(LR/LS) and Yb(dbm)3(C2H5OH) moieties in which the two YbIII ions are eight and seven-coordinated, respectively. They not only feature different molecular structures but also present distinct linear and nonlinear optical performances. Chiral mononuclear D-1 has better near infrared photo-luminescence (NIR-PL) and circularly polarized luminescence (CPL) performances than chiral cocrystal D-2. More remarkably, D-1/L-1 show large second-harmonic generation (SHG) responses (up to 1.25/1.28 × KDP) 18/16 times those of D-2/L-2 (0.07/0.08 × KDP). In addition, D-2/L-2 represent the first examples of lanthanide cocrystal complexes with NIR-PL, NIR-CPL and SHG properties.
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.