Pawel J. Bonarek, Mikolaj Zychowicz, Jan Rzepiela, Michal Liberka, Sebastian Baś, Jakub J. Zakrzewski, Szymon Chorazy
{"title":"Design of DyIII single-molecule magnets with molecularly installed luminescent thermometers based on bridging [PtII(CN)2(C^N)]– complexes","authors":"Pawel J. Bonarek, Mikolaj Zychowicz, Jan Rzepiela, Michal Liberka, Sebastian Baś, Jakub J. Zakrzewski, Szymon Chorazy","doi":"10.1039/d4qi02373k","DOIUrl":null,"url":null,"abstract":"Luminescent Single-Molecule Magnets (SMMs) gained broad scientific attention due to potential applications in dual sensing of temperature and magnetic field or optical thermometry for the self-monitoring of temperature in SMM-based devices. We present a route toward thermoresponsive emissive SMMs based on linking two molecular components separately providing luminescent thermometry and SMM features. We combined Dy(III) centers of a rationally constrained coordination sphere giving tunable magnetic anisotropy with an emissive dicyanido(2-phenylpyridinato)platinate(II) anion, [Pt<small><sup>II</sup></small>(CN)<small><sub>2</sub></small>(ppy)]<small><sup>–</sup></small> exhibiting ratiometric optical thermometry. These molecular precursors undergo the self-assembly into {[Dy<small><sup>III</sup></small>(MeOH)<small><sub>2</sub></small>(NO<small><sub>3</sub></small>)]<small><sub>2</sub></small>[Pt<small><sup>II</sup></small>(CN)<small><sub>2</sub></small>(ppy)]<small><sub>4</sub></small>}∙<em>n</em>(solvent) (<strong>1</strong>) coordination chains of a weak field-induced SMM behavior. However, upon exchange of MeOH molecules, axially aligned within eight-coordinated Dy(III) complexes, by O-donor organic ligands, including 4(1H)-pyridone (<strong>2</strong>), pyridazin-4(1H)-one (<strong>3</strong>), and N-methyl-pyridin-4(1H)-one (<strong>4</strong>), an improvement of SMM character was achieved. This is accompanied by the tuning of optical thermometry related to temperature-variable excitation and emission spectra of Pt(II) complexes which leads to the best-performance multifunctionality in a 4(1H)-pyridone-containing compound. Our work proves that a heterometallic synthetic approach provides a unique class of SMM-based luminescent thermometers where lanthanide-centered magnetism will not be affected by the light employed to monitor the temperature through an optical process occurring in attached cyanido transition metal complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1000,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4qi02373k","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Luminescent Single-Molecule Magnets (SMMs) gained broad scientific attention due to potential applications in dual sensing of temperature and magnetic field or optical thermometry for the self-monitoring of temperature in SMM-based devices. We present a route toward thermoresponsive emissive SMMs based on linking two molecular components separately providing luminescent thermometry and SMM features. We combined Dy(III) centers of a rationally constrained coordination sphere giving tunable magnetic anisotropy with an emissive dicyanido(2-phenylpyridinato)platinate(II) anion, [PtII(CN)2(ppy)]– exhibiting ratiometric optical thermometry. These molecular precursors undergo the self-assembly into {[DyIII(MeOH)2(NO3)]2[PtII(CN)2(ppy)]4}∙n(solvent) (1) coordination chains of a weak field-induced SMM behavior. However, upon exchange of MeOH molecules, axially aligned within eight-coordinated Dy(III) complexes, by O-donor organic ligands, including 4(1H)-pyridone (2), pyridazin-4(1H)-one (3), and N-methyl-pyridin-4(1H)-one (4), an improvement of SMM character was achieved. This is accompanied by the tuning of optical thermometry related to temperature-variable excitation and emission spectra of Pt(II) complexes which leads to the best-performance multifunctionality in a 4(1H)-pyridone-containing compound. Our work proves that a heterometallic synthetic approach provides a unique class of SMM-based luminescent thermometers where lanthanide-centered magnetism will not be affected by the light employed to monitor the temperature through an optical process occurring in attached cyanido transition metal complexes.