{"title":"由(R)/(S)-2-甲氧基-2-苯基乙酸衍生的同手性Dy2Zn2零场单分子磁体","authors":"Cai-Ming Liu, Xiang Hao and Yi-Quan Zhang","doi":"10.1039/D5DT01609F","DOIUrl":null,"url":null,"abstract":"<p >Despite the unique advantages of multifunctional integration at the nanoscale, chiral zero-field single-molecule magnets (SMMs), especially those based on homochiral carboxylic acids, are still difficult to obtain. Herein, homochiral (<em>R</em>)/(<em>S</em>)-2-methoxy-2-phenylacetic acids (<em>R</em>-HMPA)/(<em>S</em>-HMPA) were selected as the bridging ligands to assemble a pair of Dy<small><sub>2</sub></small>Zn<small><sub>2</sub></small> enantiomers based on the Schiff base ligand (<em>E</em>)-2-((2-hydroxy-3-methoxybenzylidene)amino)phenol (H<small><sub>2</sub></small>L<small><sub>Schiff</sub></small>), [Dy<small><sub>2</sub></small>Zn<small><sub>2</sub></small>(<em>S</em>-MPA)<small><sub>2</sub></small>(L<small><sub>Schiff</sub></small>)<small><sub>4</sub></small>(DMF)<small><sub>2</sub></small>]·2DMF (<em>S</em>-<strong>1</strong>) (DMF = <em>N</em>,<em>N</em>-dimethylformamide) and [Dy<small><sub>2</sub></small>Zn<small><sub>2</sub></small>(<em>R</em>-MPA)<small><sub>2</sub></small>(L<small><sub>Schiff</sub></small>)<small><sub>4</sub></small>(DMF)<small><sub>2</sub></small>]·2DMF (<em>R</em>-<strong>1</strong>), which possess a [Dy<small><sub>2</sub></small>Zn<small><sub>2</sub></small>O<small><sub>6</sub></small>] defective dicubane core. The CD spectra of <em>R</em>-<strong>1</strong> and <em>S</em>-<strong>1</strong> confirmed their enantiomeric nature and chiral optical activities. Magnetic studies revealed that they are good zero-field SMMs, with a relatively large <em>U</em><small><sub>eff</sub></small>/<em>k</em> value of 234.6 K at 0 Oe and an obvious hysteresis loop at 3.0 K; notably, these magnetic properties could be explained using <em>ab initio</em> calculations.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 36","pages":" 13522-13528"},"PeriodicalIF":3.3000,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d5dt01609f?page=search","citationCount":"0","resultStr":"{\"title\":\"Homochiral Dy2Zn2 zero-field single-molecule magnets derived from (R)/(S)-2-methoxy-2-phenylacetic acids\",\"authors\":\"Cai-Ming Liu, Xiang Hao and Yi-Quan Zhang\",\"doi\":\"10.1039/D5DT01609F\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Despite the unique advantages of multifunctional integration at the nanoscale, chiral zero-field single-molecule magnets (SMMs), especially those based on homochiral carboxylic acids, are still difficult to obtain. Herein, homochiral (<em>R</em>)/(<em>S</em>)-2-methoxy-2-phenylacetic acids (<em>R</em>-HMPA)/(<em>S</em>-HMPA) were selected as the bridging ligands to assemble a pair of Dy<small><sub>2</sub></small>Zn<small><sub>2</sub></small> enantiomers based on the Schiff base ligand (<em>E</em>)-2-((2-hydroxy-3-methoxybenzylidene)amino)phenol (H<small><sub>2</sub></small>L<small><sub>Schiff</sub></small>), [Dy<small><sub>2</sub></small>Zn<small><sub>2</sub></small>(<em>S</em>-MPA)<small><sub>2</sub></small>(L<small><sub>Schiff</sub></small>)<small><sub>4</sub></small>(DMF)<small><sub>2</sub></small>]·2DMF (<em>S</em>-<strong>1</strong>) (DMF = <em>N</em>,<em>N</em>-dimethylformamide) and [Dy<small><sub>2</sub></small>Zn<small><sub>2</sub></small>(<em>R</em>-MPA)<small><sub>2</sub></small>(L<small><sub>Schiff</sub></small>)<small><sub>4</sub></small>(DMF)<small><sub>2</sub></small>]·2DMF (<em>R</em>-<strong>1</strong>), which possess a [Dy<small><sub>2</sub></small>Zn<small><sub>2</sub></small>O<small><sub>6</sub></small>] defective dicubane core. The CD spectra of <em>R</em>-<strong>1</strong> and <em>S</em>-<strong>1</strong> confirmed their enantiomeric nature and chiral optical activities. Magnetic studies revealed that they are good zero-field SMMs, with a relatively large <em>U</em><small><sub>eff</sub></small>/<em>k</em> value of 234.6 K at 0 Oe and an obvious hysteresis loop at 3.0 K; notably, these magnetic properties could be explained using <em>ab initio</em> calculations.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 36\",\"pages\":\" 13522-13528\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-08-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d5dt01609f?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d5dt01609f\",\"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/d5dt01609f","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Homochiral Dy2Zn2 zero-field single-molecule magnets derived from (R)/(S)-2-methoxy-2-phenylacetic acids
Despite the unique advantages of multifunctional integration at the nanoscale, chiral zero-field single-molecule magnets (SMMs), especially those based on homochiral carboxylic acids, are still difficult to obtain. Herein, homochiral (R)/(S)-2-methoxy-2-phenylacetic acids (R-HMPA)/(S-HMPA) were selected as the bridging ligands to assemble a pair of Dy2Zn2 enantiomers based on the Schiff base ligand (E)-2-((2-hydroxy-3-methoxybenzylidene)amino)phenol (H2LSchiff), [Dy2Zn2(S-MPA)2(LSchiff)4(DMF)2]·2DMF (S-1) (DMF = N,N-dimethylformamide) and [Dy2Zn2(R-MPA)2(LSchiff)4(DMF)2]·2DMF (R-1), which possess a [Dy2Zn2O6] defective dicubane core. The CD spectra of R-1 and S-1 confirmed their enantiomeric nature and chiral optical activities. Magnetic studies revealed that they are good zero-field SMMs, with a relatively large Ueff/k value of 234.6 K at 0 Oe and an obvious hysteresis loop at 3.0 K; notably, these magnetic properties could be explained using ab initio calculations.
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.