Xiedong Cheng, Feifan Li, Qingqing Huang, Laura C. J. Pereira, Rui Cui, Yaping Li and Minfeng Lü
{"title":"Synthesis, structures, and magnetic properties of alkali metal manganese(iii) fluorophosphates containing low-dimensional S = 2 spin structures†","authors":"Xiedong Cheng, Feifan Li, Qingqing Huang, Laura C. J. Pereira, Rui Cui, Yaping Li and Minfeng Lü","doi":"10.1039/D4DT02768J","DOIUrl":null,"url":null,"abstract":"<p >Five alkali metal manganese(<small>III</small>) fluorophosphates, K<small><sub>2</sub></small>Mn(PO<small><sub>3</sub></small>F)F<small><sub>3</sub></small> (<strong>I</strong>), Rb<small><sub>2</sub></small>Mn(PO<small><sub>3</sub></small>F)F<small><sub>3</sub></small> (<strong>II</strong>), Rb<small><sub>2</sub></small>Mn<small><sub>2</sub></small>(PO<small><sub>3</sub></small>F)(PO<small><sub>4</sub></small>)F<small><sub>3</sub></small> (<strong>III</strong>), Rb<small><sub>3</sub></small>Mn<small><sub>3</sub></small>(PO<small><sub>3</sub></small>F)<small><sub>2</sub></small>(PO<small><sub>4</sub></small>)F<small><sub>5</sub></small> (<strong>IV</strong>), and CsMn(PO<small><sub>3</sub></small>F)F<small><sub>2</sub></small> (<strong>V</strong>), were successfully synthesized using a hydrothermal method. The monofluorophosphate anion (PO<small><sub>3</sub></small>F)<small><sup>2−</sup></small> groups work as “chemical scissors” to promote low-dimensional spin structures with the aid of alkali metal cations. <strong>I</strong> and <strong>II</strong> had an <em>S</em> = 2 uniform chain structure formed by corner-sharing <em>trans</em>-MnO<small><sub>2</sub></small>F<small><sub>4</sub></small> octahedra. <strong>III</strong> contained a quasi one-dimensional <em>S</em> = 2 spin chain composed of <em>trans</em>-MnO<small><sub>4</sub></small>F<small><sub>2</sub></small> octahedra and <em>trans</em>-MnO<small><sub>2</sub></small>F<small><sub>4</sub></small> octahedra through vertex-sharing fluorine atoms running along the [1−10] direction, whereas <strong>V</strong> exhibited a zigzag <em>S</em> = 2 spin chain built from the <em>facial</em>-MnO<small><sub>3</sub></small>F<small><sub>3</sub></small> octahedron. In contrast, <strong>IV</strong> constitutes weakly coupled <em>S</em> = 2 spin trimers, where the three-dimensional (3D) framework contains two-dimensional {Mn<small><sub>3</sub></small>O<small><sub>4</sub></small>F<small><sub>4</sub></small>(PO<small><sub>3</sub></small>F)<small><sub>2</sub></small>}<small><sup>2−</sup></small> layers formed by trinuclear Mn-octahedral units <em>via</em> corner-sharing fluorine atoms separated by PO<small><sub>3</sub></small>F tetrahedra. Magnetic measurements confirmed that <strong>I</strong> and <strong>II</strong> possess antiferromagnetic (AFM) long-range ordering at low temperature, with intrachain exchange couplings <em>J</em><small><sub>intra</sub></small>/<em>k</em><small><sub>B</sub></small> = −12.1(1) K for <strong>I</strong> and <em>J</em><small><sub>intra</sub></small>/<em>k</em><small><sub>B</sub></small> = −8.1(2) K for <strong>II</strong>. The magnetic behaviour of <strong>IV</strong> was very complex, with three successive magnetic transitions owing to weak AFM coupling among <em>S</em> = 2 spin trimers. <strong>V</strong> shows an alternating <em>S</em> = 2 one-dimensional (1D) chain with canted AFM ordering at 16.5 K.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 8","pages":" 3486-3499"},"PeriodicalIF":3.5000,"publicationDate":"2025-01-27","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/d4dt02768j","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
Five alkali metal manganese(III) fluorophosphates, K2Mn(PO3F)F3 (I), Rb2Mn(PO3F)F3 (II), Rb2Mn2(PO3F)(PO4)F3 (III), Rb3Mn3(PO3F)2(PO4)F5 (IV), and CsMn(PO3F)F2 (V), were successfully synthesized using a hydrothermal method. The monofluorophosphate anion (PO3F)2− groups work as “chemical scissors” to promote low-dimensional spin structures with the aid of alkali metal cations. I and II had an S = 2 uniform chain structure formed by corner-sharing trans-MnO2F4 octahedra. III contained a quasi one-dimensional S = 2 spin chain composed of trans-MnO4F2 octahedra and trans-MnO2F4 octahedra through vertex-sharing fluorine atoms running along the [1−10] direction, whereas V exhibited a zigzag S = 2 spin chain built from the facial-MnO3F3 octahedron. In contrast, IV constitutes weakly coupled S = 2 spin trimers, where the three-dimensional (3D) framework contains two-dimensional {Mn3O4F4(PO3F)2}2− layers formed by trinuclear Mn-octahedral units via corner-sharing fluorine atoms separated by PO3F tetrahedra. Magnetic measurements confirmed that I and II possess antiferromagnetic (AFM) long-range ordering at low temperature, with intrachain exchange couplings Jintra/kB = −12.1(1) K for I and Jintra/kB = −8.1(2) K for II. The magnetic behaviour of IV was very complex, with three successive magnetic transitions owing to weak AFM coupling among S = 2 spin trimers. V shows an alternating S = 2 one-dimensional (1D) chain with canted AFM ordering at 16.5 K.
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.