Structure and Magnetism of an Ideal One-Dimensional Chain Antiferromagnet [C2NH8]3[Fe(SO4)3] with a Large Spin of S = 5/2

Li, Mingyang; Ouyang, Zhongwen; Liu, Xiaochen; Cao, Jiaojiao; Xiao, Tongtong; Xiao, Guangqin; Wang, Zhenxing

doi:10.1021/acs.inorgchem.2c02001

Cited by 4 publications

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“…T N / T max is often used as a measure of the one-dimensionality of magnetic materials. The values of T N / T max are 0.01 for (4,4′-bpy)FeF 3 , 0.02 for [(CH 3 ) 4 N]MnCl 3 , 0.11 for [C 2 NH 8 ] 3 [Fe(SO 4 ) 3 ], 0.80 for CuMnVO 4 , and 0.04 in inter-1 , and all of the other reported compounds with 1D S = 5/2 chains have much higher values (Table S6). The present study shows that T N / T max in 1 is less than 0.004, which is 1 order of magnitude smaller.…”

Section: Discussionmentioning

confidence: 96%

“…To estimate J ′, a model based on Green function method, which is more appropriate for small J ′/ J , k B T N /| J | = 4 S ( S + 1)/3 I ( η ), was employed, where I ( η ) ≈ 0.633/( η 1/2 ), η = J ′/ J . We found that the value of J ′/ J for 1 is smaller than 3.27 × 10 –6 . It is 10 times smaller than that of (4,4′-bpy)FeF 3 , 1000 times smaller than [C 2 NH 8 ] 3 [Fe(SO 4 ) 3 ] (see Table S6 for further comparison). Note that it is impossible to precisely determine the origin of interactions between chains (Figure S10).…”

Section: Discussionmentioning

confidence: 98%

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Construction of Ideal One-Dimensional Spin Chains by Topochemical Dehydration/Rehydration Route

Wang,

Fu,

Takatsu

et al. 2024

J. Am. Chem. Soc.

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One-dimensional (1D) Heisenberg antiferromagnets are of great interest due to their intriguing quantum phenomena. However, the experimental realization of such systems with large spin S remains challenging because even weak interchain interactions induce long-range ordering. In this study, we present an ideal 1D S = 5/2 spin chain antiferromagnet achieved through a multistep topochemical route involving dehydration and rehydration. By desorbing three water molecules from (2,2′-bpy)-FeF 3 (H 2 O)•2H 2 O (2,2′-bpy = 2,2′-bipyridyl) at 150 °C and then intercalating two water molecules at room temperature (giving (2,2′-bpy)FeF 3 •2H 2 O 1), the initially isolated FeF 3 ON 2 octahedra combine to form corner-sharing FeF 4 N 2 octahedral chains, which are effectively separated by organic and added water molecules. Mossbauer spectroscopy reveals significant dynamical fluctuations down to 2.7 K, despite the presence of strong intrachain interactions. Moreover, results from electron spin resonance (ESR) and heat capacity measurements indicate the absence of longrange order down to 0.5 K. This controlled topochemical dehydration/rehydration approach is further extended to (2,2′-bpy)CrF 3 • 2H 2 O with S = 3/2 1D chains, thus opening the possibility of obtaining other low-dimensional spin lattices.

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Section: Discussionmentioning

confidence: 96%

Section: Discussionmentioning

confidence: 98%

Construction of Ideal One-Dimensional Spin Chains by Topochemical Dehydration/Rehydration Route

Wang,

Fu,

Takatsu

et al. 2024

J. Am. Chem. Soc.

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“…The guanidinium cation [C(NH 2 ) 3 ] + is a planar and strongly basic template and a potential donor of up to six relatively strong hydrogen bonds; it is actively employed in the synthesis of organo-inorganic compounds, − including noncentrosymmetric structures. , When considering iron organo-inorganic compounds, magnetic properties also are an important focus of the scientific research. − In this regard, of essential interest are the cation-ordered structures incorporating both Fe II ( S = 2) and Fe III ( S = 5/2). Among sulfate minerals, such Fe II /Fe III ordering has been reported for römerite, Fe II Fe III 2 (SO 4 ) 4 ·14H 2 O, and voltaite, K 2 Fe II 5 Fe III 3 Al(SO 4 ) 12 ·18H 2 O .…”

Section: Introductionmentioning

confidence: 99%

(CN₃H₆)[Fe^IIFe^III(SO₄)₃(H₂O)₃]: A Framework Iron Sulfate with a Mixed S = 2 and S = 5/2 Honeycomb Lattice

Ginga,

Siidra,

Tsirlin

et al. 2023

Inorg. Chem.

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A new guanidinium-templated hydrated iron sulfate, [CN 3 H 6 ][Fe II Fe III (SO 4 ) 3 (H 2 O) 3 ] (1), was prepared from strongly acidic aqueous solutions. Its crystal structure is comprised from Fe III O 6 and Fe II O 3 (H 2 O) 3 octahedra linked by sulfate bridges forming a [Fe II Fe II (SO 4 ) 3 (H 2 O) 3 ] − 3D framework with a layer-bylayer ordering of ferric and ferrous cations. The structural topology of the framework is related to the anhydrous rhombohedral mikasaite Fe 2 (SO 4 ) 3 . The removal of part of the sulfate tetrahedra and the partial replacement of the Fe 3+ cations in the [Fe 3+2 (SO 4 ) 3 ] 0 framework by Fe 2+ provide a negative charge and allow the incorporation of the protonated organic species in the voids. The compound 1 has been characterized by single-crystal Xray diffraction, TG and DSC analyses, UV−vis−NIR spectroscopy, magnetic susceptibility, Mossbauer spectroscopy, IR and Raman spectroscopy, and density functional band-structure calculations. The magnetic behavior of 1 shows an interplay of Fe II (S = 2) and Fe III (S = 5/2) sublattices that exhibit different types of antiferromagnetic couplings, one Fe III −Fe III (J 1 ∼ 6.1 K) and two Fe II −Fe III couplings (J 2 ∼ 1 K, J 3 ∼ 5.9 K) within corrugated honeycomb layers. These ferrimagnetic layers are coupled antiparallel to each other, resulting in an overall antiferromagnetic order below T N = 31 K.

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Single‐Step Synthesis of An Ideal Chain Antiferromagnet [H₂(4,4′‐bipyridyl)](H₃O)₂Fe₂F₁₀ with Spin S=5/2

Wang,

Dou,

Takastu

et al. 2024

Angewandte Chemie

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One‐dimensional (1D) magnets are of great interest owing to their intriguing quantum phenomena and potential application in quantum computing. We successfully synthesized an ideal antiferromagnetic spin S=5/2 chain compound [H2(4,4′‐bpy)](H3O)2Fe2F10 (4,4′‐bpy=4,4′‐bipyridyl) 1, using a single‐step low‐temperature hydrothermal method under conditions that favors the protonation of the bulky bidentate ligand 4,4′‐bpy. Compound 1 consists of well‐separated (Fe3+−F−)∞ chains with a large Fe−F−Fe angle of 174.8°. Both magnetic susceptibility and specific heat measurements show that 1 does not undergo a magnetic long‐range ordering down to 0.5 K, despite the strong Fe−F−Fe intrachain spin exchange J with J/kB=−16.2(1) K. This indicates a negligibly weak interchain spin exchange J′. The J′/J value estimated for 1 is extremely small (<2.8×10−6), smaller than those reported for all other S=5/2 chain magnets. Our hydrothermal synthesis incorporates both [H2(4,4′‐bpy)]2+ and (H3O)+ cations into the crystal lattice with numerous hydrogen bonds, hence effectively separating the (Fe3+−F−)∞ spin chains. This single‐step hydrothermal synthesis under conditions favoring the protonation of bulky bidentate ligands offers an effective synthetic strategy to prepare well‐separated 1D spin chain systems of magnetic ions with various spin values.

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Structure and Magnetism of an Ideal One-Dimensional Chain Antiferromagnet [C₂NH₈]₃[Fe(SO₄)₃] with a Large Spin of S = 5/2

Cited by 4 publications

References 41 publications

Construction of Ideal One-Dimensional Spin Chains by Topochemical Dehydration/Rehydration Route

Construction of Ideal One-Dimensional Spin Chains by Topochemical Dehydration/Rehydration Route

(CN₃H₆)[Fe^IIFe^III(SO₄)₃(H₂O)₃]: A Framework Iron Sulfate with a Mixed S = 2 and S = 5/2 Honeycomb Lattice

Single‐Step Synthesis of An Ideal Chain Antiferromagnet [H₂(4,4′‐bipyridyl)](H₃O)₂Fe₂F₁₀ with Spin S=5/2

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Structure and Magnetism of an Ideal One-Dimensional Chain Antiferromagnet [C2NH8]3[Fe(SO4)3] with a Large Spin of S = 5/2

Cited by 4 publications

References 41 publications

Construction of Ideal One-Dimensional Spin Chains by Topochemical Dehydration/Rehydration Route

Construction of Ideal One-Dimensional Spin Chains by Topochemical Dehydration/Rehydration Route

(CN3H6)[FeIIFeIII(SO4)3(H2O)3]: A Framework Iron Sulfate with a Mixed S = 2 and S = 5/2 Honeycomb Lattice

Single‐Step Synthesis of An Ideal Chain Antiferromagnet [H2(4,4′‐bipyridyl)](H3O)2Fe2F10 with Spin S=5/2

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Structure and Magnetism of an Ideal One-Dimensional Chain Antiferromagnet [C₂NH₈]₃[Fe(SO₄)₃] with a Large Spin of S = 5/2

(CN₃H₆)[Fe^IIFe^III(SO₄)₃(H₂O)₃]: A Framework Iron Sulfate with a Mixed S = 2 and S = 5/2 Honeycomb Lattice

Single‐Step Synthesis of An Ideal Chain Antiferromagnet [H₂(4,4′‐bipyridyl)](H₃O)₂Fe₂F₁₀ with Spin S=5/2