Patrick Mangundu, Kate E. Tanner, Andrew Bloomfield, Peter J. Barnard, Keith F. White, Curtis C. Ho, Nageshwar R. Yepuri, Richard A. Mole and Rebecca O. Fuller
{"title":"三核稀土吡啶基-β-二酮酸配合物：开发寻找丢失环向自旋态的新方法","authors":"Patrick Mangundu, Kate E. Tanner, Andrew Bloomfield, Peter J. Barnard, Keith F. White, Curtis C. Ho, Nageshwar R. Yepuri, Richard A. Mole and Rebecca O. Fuller","doi":"10.1039/D5DT01067E","DOIUrl":null,"url":null,"abstract":"<p >A series of rare earth (RE) ‘triangles’ have been synthesised to investigate the low energy excitations of toroic molecules using inelastic neutron scattering (INS) experiments. β-Diketonate, 1-(2-pyridinyl)-1,3-butandione (<em>o</em>-pbdH) has been employed to synthesise [{Ho<small><sub>3</sub></small>(O)<small><sub>2</sub></small>(<em>o</em>-pbd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>}<small><sub>2</sub></small>]·8Cl·3H<small><sub>2</sub></small>O·0.5EtOH (<strong>1</strong>) and [{Dy<small><sub>3</sub></small>(O)<small><sub>2</sub></small>(<em>o</em>-pbd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>}<small><sub>2</sub></small>]·6Cl·2EtOH·2hexane (<strong>2</strong>). With further examples, [Ho<small><sub>3</sub></small>(OH)<small><sub>2</sub></small>(<em>o</em>-pbd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>3</sub></small>(EtOH)<small><sub>2</sub></small>]·3Cl (<strong>3</strong>), [{Ho<small><sub>3</sub></small>(OH)<small><sub>2</sub></small>(<em>o</em>-pbd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>}<small><sub>2</sub></small>]·6Cl·2H<small><sub>2</sub></small>O (<strong>4</strong>) and [Dy<small><sub>3</sub></small>(O)(OH)(<em>o</em>-pbd)<small><sub>3</sub></small>(NO<small><sub>3</sub></small>)<small><sub>4</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]·2NO<small><sub>3</sub></small>·H<small><sub>2</sub></small>O (<strong>5</strong>) aimed towards the generation of variation in coordinated ancillary ligands that are capable of reducing symmetry and inhibiting toroic behaviour. A sterically bulky 3-(1-naphthyl)-1-(2-pyridyl)-propane-1,3-dione (<em>o</em>-nppdH) ligand impeded the formation of the RE<small><sub>3</sub></small> motif with [Dy<small><sub>2</sub></small>(O)<small><sub>2</sub></small>(<em>o</em>-nppd)<small><sub>5</sub></small>(H<small><sub>2</sub></small>O)]·6Cl (<strong>6</strong>) isolated. The RE<small><sub>3</sub></small> complexes are structurally similar to known trinuclear based single molecular toroics (SMTs), including RE-β-diketonate analogues prone to mixing between electronic states. Consistent with these, a non-magnetic SMT ground state was not observable in the new complexes utilising conventional magnetometry. Spectroscopic confirmation of toroic properties with INS was attempted for the first time on <strong>1</strong> and the structurally similar SMT [Ho<small><sub>3</sub></small>(OH)<small><sub>2</sub></small>(<em>o</em>-dppd-d<small><sub>10</sub></small>)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>]. The observed intensity of a broad Lorentzian at 0.69(1) meV for [Ho<small><sub>3</sub></small>(OH)<small><sub>2</sub></small>(<em>o</em>-dppd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>] and 0.44(1) meV for <strong>1</strong>, is remarkably close to the calculated energy gap ∼5 cm<small><sup>−1</sup></small> (or 0.62 meV) and potentially provides a new probe that can validate complexes with a poorly separated toroidic ground state.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 26","pages":" 10455-10466"},"PeriodicalIF":3.3000,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Trinuclear rare earth pyridyl-β-diketonate complexes: developing new methods towards finding lost toroidal spin states†\",\"authors\":\"Patrick Mangundu, Kate E. Tanner, Andrew Bloomfield, Peter J. Barnard, Keith F. White, Curtis C. Ho, Nageshwar R. Yepuri, Richard A. Mole and Rebecca O. Fuller\",\"doi\":\"10.1039/D5DT01067E\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A series of rare earth (RE) ‘triangles’ have been synthesised to investigate the low energy excitations of toroic molecules using inelastic neutron scattering (INS) experiments. β-Diketonate, 1-(2-pyridinyl)-1,3-butandione (<em>o</em>-pbdH) has been employed to synthesise [{Ho<small><sub>3</sub></small>(O)<small><sub>2</sub></small>(<em>o</em>-pbd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>}<small><sub>2</sub></small>]·8Cl·3H<small><sub>2</sub></small>O·0.5EtOH (<strong>1</strong>) and [{Dy<small><sub>3</sub></small>(O)<small><sub>2</sub></small>(<em>o</em>-pbd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>}<small><sub>2</sub></small>]·6Cl·2EtOH·2hexane (<strong>2</strong>). With further examples, [Ho<small><sub>3</sub></small>(OH)<small><sub>2</sub></small>(<em>o</em>-pbd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>3</sub></small>(EtOH)<small><sub>2</sub></small>]·3Cl (<strong>3</strong>), [{Ho<small><sub>3</sub></small>(OH)<small><sub>2</sub></small>(<em>o</em>-pbd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>}<small><sub>2</sub></small>]·6Cl·2H<small><sub>2</sub></small>O (<strong>4</strong>) and [Dy<small><sub>3</sub></small>(O)(OH)(<em>o</em>-pbd)<small><sub>3</sub></small>(NO<small><sub>3</sub></small>)<small><sub>4</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]·2NO<small><sub>3</sub></small>·H<small><sub>2</sub></small>O (<strong>5</strong>) aimed towards the generation of variation in coordinated ancillary ligands that are capable of reducing symmetry and inhibiting toroic behaviour. A sterically bulky 3-(1-naphthyl)-1-(2-pyridyl)-propane-1,3-dione (<em>o</em>-nppdH) ligand impeded the formation of the RE<small><sub>3</sub></small> motif with [Dy<small><sub>2</sub></small>(O)<small><sub>2</sub></small>(<em>o</em>-nppd)<small><sub>5</sub></small>(H<small><sub>2</sub></small>O)]·6Cl (<strong>6</strong>) isolated. The RE<small><sub>3</sub></small> complexes are structurally similar to known trinuclear based single molecular toroics (SMTs), including RE-β-diketonate analogues prone to mixing between electronic states. Consistent with these, a non-magnetic SMT ground state was not observable in the new complexes utilising conventional magnetometry. Spectroscopic confirmation of toroic properties with INS was attempted for the first time on <strong>1</strong> and the structurally similar SMT [Ho<small><sub>3</sub></small>(OH)<small><sub>2</sub></small>(<em>o</em>-dppd-d<small><sub>10</sub></small>)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>]. The observed intensity of a broad Lorentzian at 0.69(1) meV for [Ho<small><sub>3</sub></small>(OH)<small><sub>2</sub></small>(<em>o</em>-dppd)<small><sub>3</sub></small>Cl(H<small><sub>2</sub></small>O)<small><sub>5</sub></small>] and 0.44(1) meV for <strong>1</strong>, is remarkably close to the calculated energy gap ∼5 cm<small><sup>−1</sup></small> (or 0.62 meV) and potentially provides a new probe that can validate complexes with a poorly separated toroidic ground state.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 26\",\"pages\":\" 10455-10466\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-06-13\",\"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/d5dt01067e\",\"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/d5dt01067e","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Trinuclear rare earth pyridyl-β-diketonate complexes: developing new methods towards finding lost toroidal spin states†
A series of rare earth (RE) ‘triangles’ have been synthesised to investigate the low energy excitations of toroic molecules using inelastic neutron scattering (INS) experiments. β-Diketonate, 1-(2-pyridinyl)-1,3-butandione (o-pbdH) has been employed to synthesise [{Ho3(O)2(o-pbd)3Cl(H2O)5}2]·8Cl·3H2O·0.5EtOH (1) and [{Dy3(O)2(o-pbd)3Cl(H2O)5}2]·6Cl·2EtOH·2hexane (2). With further examples, [Ho3(OH)2(o-pbd)3Cl(H2O)3(EtOH)2]·3Cl (3), [{Ho3(OH)2(o-pbd)3Cl(H2O)5}2]·6Cl·2H2O (4) and [Dy3(O)(OH)(o-pbd)3(NO3)4(H2O)2]·2NO3·H2O (5) aimed towards the generation of variation in coordinated ancillary ligands that are capable of reducing symmetry and inhibiting toroic behaviour. A sterically bulky 3-(1-naphthyl)-1-(2-pyridyl)-propane-1,3-dione (o-nppdH) ligand impeded the formation of the RE3 motif with [Dy2(O)2(o-nppd)5(H2O)]·6Cl (6) isolated. The RE3 complexes are structurally similar to known trinuclear based single molecular toroics (SMTs), including RE-β-diketonate analogues prone to mixing between electronic states. Consistent with these, a non-magnetic SMT ground state was not observable in the new complexes utilising conventional magnetometry. Spectroscopic confirmation of toroic properties with INS was attempted for the first time on 1 and the structurally similar SMT [Ho3(OH)2(o-dppd-d10)3Cl(H2O)5]. The observed intensity of a broad Lorentzian at 0.69(1) meV for [Ho3(OH)2(o-dppd)3Cl(H2O)5] and 0.44(1) meV for 1, is remarkably close to the calculated energy gap ∼5 cm−1 (or 0.62 meV) and potentially provides a new probe that can validate complexes with a poorly separated toroidic ground state.
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.
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