Synthesis, structures, and magnetic properties of alkali metal manganese(iii) fluorophosphates containing low-dimensional S = 2 spin structures†

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Dalton Transactions Pub Date : 2025-01-27 DOI:10.1039/D4DT02768J
Xiedong Cheng, Feifan Li, Qingqing Huang, Laura C. J. Pereira, Rui Cui, Yaping Li and Minfeng Lü
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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.

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Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
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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