{"title":"由轴向手性配体(R)/(S)-八氢-1,1'-双-2-磷酸萘基衍生的同手性Dy2零场单分子磁体","authors":"Cai-Ming Liu, Xiang Hao and Yi-Quan Zhang","doi":"10.1039/D4DT03408B","DOIUrl":null,"url":null,"abstract":"<p >The construction of homochiral zero-field single-molecule magnets (SMMs), especially with axial chiral ligands, remains a great challenge. Herein the first examples of homochiral Dy(<small>III</small>) Schiff base complexes based on axial chiral ligands (<em>R</em>)/(<em>S</em>)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-bi-2-naphthyl phosphate (<em>R</em>-HL/<em>S</em>-HL), [Dy<small><sub>2</sub></small>(<em>R</em>-L/<em>S</em>-L)<small><sub>2</sub></small>(L<small><sub>Schiff</sub></small>)<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)(MeOH)]·2MeOH·CH<small><sub>2</sub></small>Cl<small><sub>2</sub></small>·2MeCN·2H<small><sub>2</sub></small>O (<em>R</em>-<strong>1</strong>/<em>S</em>-<strong>1</strong>) [H<small><sub>2</sub></small>L<small><sub>Schiff</sub></small> = (<em>E</em>)-<em>N</em>′-(5-fluoro-2-hydroxybenzylidene)pyrazine-2-carbohydrazide], were synthesized at room temperature, which show ferromagnetic coupling and act as zero-field SMMs, with a <em>U</em><small><sub>eff</sub></small>/<em>k</em> value of 61 K at 0 Oe. <em>Ab initio</em> calculations were used to explain their magnetic interaction and magnetic relaxation properties. Furthermore, the magnetic circular dichroism (MCD) spectra of <em>R</em>-<strong>1</strong>/<em>S</em>-<strong>1</strong> revealed that they display obvious magneto-optical effects.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 10","pages":" 4159-4166"},"PeriodicalIF":3.3000,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Homochiral Dy2 zero-field single-molecule magnets derived from axial chiral ligands (R)/(S)-octahydro-1,1′-bi-2-naphthyl phosphate†\",\"authors\":\"Cai-Ming Liu, Xiang Hao and Yi-Quan Zhang\",\"doi\":\"10.1039/D4DT03408B\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The construction of homochiral zero-field single-molecule magnets (SMMs), especially with axial chiral ligands, remains a great challenge. Herein the first examples of homochiral Dy(<small>III</small>) Schiff base complexes based on axial chiral ligands (<em>R</em>)/(<em>S</em>)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-bi-2-naphthyl phosphate (<em>R</em>-HL/<em>S</em>-HL), [Dy<small><sub>2</sub></small>(<em>R</em>-L/<em>S</em>-L)<small><sub>2</sub></small>(L<small><sub>Schiff</sub></small>)<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)(MeOH)]·2MeOH·CH<small><sub>2</sub></small>Cl<small><sub>2</sub></small>·2MeCN·2H<small><sub>2</sub></small>O (<em>R</em>-<strong>1</strong>/<em>S</em>-<strong>1</strong>) [H<small><sub>2</sub></small>L<small><sub>Schiff</sub></small> = (<em>E</em>)-<em>N</em>′-(5-fluoro-2-hydroxybenzylidene)pyrazine-2-carbohydrazide], were synthesized at room temperature, which show ferromagnetic coupling and act as zero-field SMMs, with a <em>U</em><small><sub>eff</sub></small>/<em>k</em> value of 61 K at 0 Oe. <em>Ab initio</em> calculations were used to explain their magnetic interaction and magnetic relaxation properties. Furthermore, the magnetic circular dichroism (MCD) spectra of <em>R</em>-<strong>1</strong>/<em>S</em>-<strong>1</strong> revealed that they display obvious magneto-optical effects.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 10\",\"pages\":\" 4159-4166\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-01-28\",\"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/2025/dt/d4dt03408b\",\"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/2025/dt/d4dt03408b","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
The construction of homochiral zero-field single-molecule magnets (SMMs), especially with axial chiral ligands, remains a great challenge. Herein the first examples of homochiral Dy(III) Schiff base complexes based on axial chiral ligands (R)/(S)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-bi-2-naphthyl phosphate (R-HL/S-HL), [Dy2(R-L/S-L)2(LSchiff)2(H2O)(MeOH)]·2MeOH·CH2Cl2·2MeCN·2H2O (R-1/S-1) [H2LSchiff = (E)-N′-(5-fluoro-2-hydroxybenzylidene)pyrazine-2-carbohydrazide], were synthesized at room temperature, which show ferromagnetic coupling and act as zero-field SMMs, with a Ueff/k value of 61 K at 0 Oe. Ab initio calculations were used to explain their magnetic interaction and magnetic relaxation properties. Furthermore, the magnetic circular dichroism (MCD) spectra of R-1/S-1 revealed that they display obvious magneto-optical effects.
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.