{"title":"First TPymT-Ln complexes (TPymT = 2,4,6-Tris(2-pyrimidyl)-1,3,5-triazine; Ln = Eu, Gd, Tb, Dy): Solvothermal synthesis, structure, magnetic and photoluminescent properties","authors":"Burak Ay , Rina Takano , Takayuki Ishida","doi":"10.1016/j.solidstatesciences.2024.107723","DOIUrl":null,"url":null,"abstract":"<div><div>Four novel mononuclear lanthanide complexes, [Ln(<strong>TPymT</strong>)(NO<sub>3</sub>)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>] (Ln: Eu<sup>3+</sup> (<strong>1</strong>), Gd<sup>3+</sup> (<strong>2</strong>), Tb<sup>3+</sup> (<strong>3</strong>) and Dy<sup>3+</sup> (<strong>4</strong>)), have been solvothermally synthesized using multidentate 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (<strong>TPymT</strong>). Compounds <strong>1</strong>–<strong>3</strong> have been characterized by means of elemental analysis, FT-IR, and single-crystal/powder X-ray diffraction analysis. Compound <strong>4</strong> was structurally characterized. The Ln<sup>3+</sup> ion in <strong>1</strong>–<strong>4</strong> is ten-coordinated, where <strong>TPymT</strong> serves as an N<sub>3</sub> donor in an isostructural series. The alternating-current magnetic studies showed frequency dependence below ca. 10 K for <strong>3</strong>, as an indication of a single-ion magnet. The activation energy for the magnetization reorientation was estimated as <em>U</em><sub>eff</sub>/<em>k</em><sub>B</sub> = 95(9) K after applying a dc bias field 2000 Oe for <strong>3</strong>. The photoluminescent studies clarified that <strong>1</strong> and <strong>3</strong> behaved as red and green light emitters with quantum yields as high as 17 and 39 %, respectively. The TD-DFT calculation supports the energy level scheme of ground and excited states of <strong>TPymT</strong> together with the reference compound 4′-phenyl-2,2’:6′,2″-terpyridine. The present work suggests a broad chance and motivation to apply <strong>TPymT</strong> to the field of 4f coordination chemistry.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107723"},"PeriodicalIF":3.4000,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Solid State Sciences","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1293255824002887","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Four novel mononuclear lanthanide complexes, [Ln(TPymT)(NO3)3(H2O)2] (Ln: Eu3+ (1), Gd3+ (2), Tb3+ (3) and Dy3+ (4)), have been solvothermally synthesized using multidentate 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT). Compounds 1–3 have been characterized by means of elemental analysis, FT-IR, and single-crystal/powder X-ray diffraction analysis. Compound 4 was structurally characterized. The Ln3+ ion in 1–4 is ten-coordinated, where TPymT serves as an N3 donor in an isostructural series. The alternating-current magnetic studies showed frequency dependence below ca. 10 K for 3, as an indication of a single-ion magnet. The activation energy for the magnetization reorientation was estimated as Ueff/kB = 95(9) K after applying a dc bias field 2000 Oe for 3. The photoluminescent studies clarified that 1 and 3 behaved as red and green light emitters with quantum yields as high as 17 and 39 %, respectively. The TD-DFT calculation supports the energy level scheme of ground and excited states of TPymT together with the reference compound 4′-phenyl-2,2’:6′,2″-terpyridine. The present work suggests a broad chance and motivation to apply TPymT to the field of 4f coordination chemistry.
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