Uncovering the S=12 Kagome Ferromagnet within a Family of Metal–Organic Frameworks

Ivko, Samuel; Tustain, Katherine; Dolling, Tristan; Abdeldaim, Aly H.; Mustonen, Otto; Manuel, Pascal; Wang, Chennan; Luetkens, H.; Clark, L. Pierce

doi:10.1021/acs.chemmater.2c00289

Cited by 5 publications

(6 citation statements)

References 76 publications

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“…More recently, MOF glasses, a disordered form of MOFs, are finding niche applications. This virtual collection catalogues recent MOF advances featured in Chemistry of Materials from 2022 to 2023, − with an accompanying editorial by Laura Gagliardi and Omar Yaghi that outlines three critical future directions for MOFs …”

Section: Opening Remarksmentioning

confidence: 99%

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The Chemistry of Metal Organic Framework Materials

Skrabalak

Vaidhyanathan

2023

Chem. Mater.

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The journal started its 35th year by celebrating 35 recent manuscripts in a virtual issue that highlighted diverse materialsbased research: battery materials, MXenes and layered dichalcogenides, covalent organic frameworks and porous materials, hydrogels, catalysts, photovoltaics and thermoelectrics, luminescent and optical materials, and materials discovery. The subsequent virtual issue on π-Conjugated Materials accentuated how chemical structure and conjugation can shape materials for various applications. Continuing with the theme of designable crystalline materials, we now look at Metal Organic Frameworks (MOFs), whose structure− property investigations have consistently embellished the pages of Chemistry of Materials and advanced their applications. In the last three decades, MOFs have been established as excellent candidates for interlacing complementary functions to realize high surface area materials for molecular separations and gas storage, stimuli-responsive and dynamic crystalline frameworks, and conductive crystalline porous structures. More recently, MOF glasses, a disordered form of MOFs, are finding niche applications. This virtual collection catalogues recent MOF advances featured in Chemistry of Materials from 2022 to 2023, 1−37 with an accompanying editorial by Laura Gagliardi and Omar Yaghi that outlines three critical future directions for MOFs. 38

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Section: Opening Remarksmentioning

confidence: 99%

“…Magnetic Kagome lattices are tremendously interesting but rare in MOFs. Clark and co-workers describe a family of copper carbonate based pillared-layered ferromagnetic–antiferromagnetic Kagome networks which could represent important models for pursuing novel quantum and topological states of matter …”

Section: Structural Design Transformation and Engineeringmentioning

confidence: 99%

The Chemistry of Metal Organic Framework Materials

Skrabalak

Vaidhyanathan

2023

Chem. Mater.

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“…4,5 In general, MOFs can exhibit a whole range of magnetic properties including 3D Hoffman complexes in diamagnetic or paramagnetic states, 6 standard ferromagnetism, 7 itinerant ferromagnetism, 8 or antiferromagnetism. 9 The last one has been recently reported to occur on S = 1/2 Kagome networks with Cu 2+ coordination ions with 2D layers of magnetic moments sandwiched between organic linkers. Moreover, many of them manifest a spin-switching effect also known as spin crossover (SCO), which is a transition between the lowspin (LS) state and the high-spin (HS) state induced by various stimuli such as light, temperature, pressure, and chemical reaction.…”

Section: Introductionmentioning

confidence: 99%

“…In general, MOFs can exhibit a whole range of magnetic properties including 3D Hoffman complexes in diamagnetic or paramagnetic states, standard ferromagnetism, itinerant ferromagnetism, or antiferromagnetism . The last one has been recently reported to occur on S = 1/2 Kagome networks with Cu 2+ coordination ions with 2D layers of magnetic moments sandwiched between organic linkers.…”

Section: Introductionmentioning

confidence: 99%

Spin-Resolved Band Structure of Hoffman Clathrate [Fe(pz)₂Pt(CN)₄] as an Essential Tool to Predict Optical Spectra of Metal–Organic Frameworks

Olejnik

Kopeć

Maskowicz

et al. 2023

ACS Appl. Mater. Interfaces

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Paramount spin-crossover properties of the 3D-Hoffman metalorganic framework (MOF) [Fe(pz)2Pt(CN)4] are generally described on the basis of the ligand field theory, which provides adequate insight into theoretical and simulation analysis of spintronic complexes. However, the ligand field approximation does not take into account the 3D periodicity of the actual complex lattice and surface effects and therefore cannot predict a full-scale periodic structure without utilizing more advanced methods. Therefore, in this paper, the electronic properties of the exemplar MOF were analyzed from the band structure perspective in low-spin (LS) and high-spin (HS) states. The density-of-states spectra determined for both spin-up and spin-down electrons of Fe d6 orbitals indicate spin–orbital splitting and delocalization for HS due to spin polarization in the iron atom ligand field. Presence of the surface states in the real crystal causes a red shift of the metal–metal charge transfer (MMCT) and metal–ligand charge transfer (MLCT) peaks for both HS and LS states. The addition of residual water molecules and disorder among the pyrazine rings reveal additional influences on the positions of the pyrazine band and, therefore, on the absorption spectra of the crystal. The results show a magnification of the peak correlated with the MLCT in the HS state and a significant red shift of the LS characteristic absorption band. The presented approach involving band structure analysis delivers a more complete image of the electronic properties of the [Fe(pz)2Pt(CN)4] crystalline network and can be a landmark for insightful studies of other MOFs.

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“…We note that the zinc-substituted synthetic barlowite, Zn x Cu 4– x (OH) 6 FBr, is another leading material with characteristic QSL properties . Also, some copper-based metal organic frameworks (MOFs) with kagome lattices have been synthesized. , The flexibility and complexity of the organic linkers in these MOFs require comprehensive structural studies in order to fully describe the observed magnetic properties.…”

Section: Introductionmentioning

confidence: 99%

Ground-State Spin Dynamics in d¹ Kagome-Lattice Titanium Fluorides

et al. 2022

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Many quantum magnetic materials suffer from structural imperfections. The effects of structural disorder on bulk properties are difficult to assess systematically from a chemical perspective due to the complexities of chemical synthesis. The recently reported S = 1/2 kagome lattice antiferromagnet, (CH 3 NH 3 ) 2 NaTi 3 F 12 , 1-Ti, with highly symmetric kagome layers and disordered interlayer methylammonium cations, shows no magnetic ordering down to 0.1 K. To study the impact of structural disorder in the titanium fluoride kagome compounds, (CH 3 NH 3 ) 2 KTi 3 F 12 , 2-Ti, was prepared. It presents no detectable structural disorder and only a small degree of distortion of the kagome lattice. The methylammonium disorder model of 1-Ti and order in 2-Ti were confirmed by atomic-resolution transmission electron microscopy. The antiferromagnetic interactions and band structures of both compounds were calculated based on spin-polarized density functional theory and support the magnetic structure analysis. Three spin-glass-like (SGL) transitions were observed in 2-Ti at 0.5, 1.4, and 2.3 K, while a single SGL transition can be observed in 1-Ti at 0.8 K. The absolute values of the Curie−Weiss temperatures of both 1-Ti (−139.5(7) K) and 2-Ti (−83.5(7) K) are larger than the SGL transition temperatures, which is indicative of geometrically frustrated spin glass (GFSG) states. All the SGL transitions are quenched with an applied field >0.1 T, which indicates novel magnetic phases emerge under small applied magnetic fields. The well-defined structure and the lack of structural disorder in 2-Ti suggest that 2-Ti is an ideal model compound for studying GFSG states and the potential transitions between spin liquid and GFSG states.

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Uncovering the S=12 Kagome Ferromagnet within a Family of Metal–Organic Frameworks

Abstract: Kagome networks of ferromagnetically or antiferromagnetically coupled S 1 2 1 2= ferromagnetic kagome layers that are coupled antiferromagnetically via their extended organic pillaring linkers.

Cited by 5 publications

References 76 publications

The Chemistry of Metal Organic Framework Materials

The Chemistry of Metal Organic Framework Materials

Spin-Resolved Band Structure of Hoffman Clathrate [Fe(pz)₂Pt(CN)₄] as an Essential Tool to Predict Optical Spectra of Metal–Organic Frameworks

Ground-State Spin Dynamics in d¹ Kagome-Lattice Titanium Fluorides

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Uncovering the S=12 Kagome Ferromagnet within a Family of Metal–Organic Frameworks

Abstract: Kagome networks of ferromagnetically or antiferromagnetically coupled S 1 2 1 2= ferromagnetic kagome layers that are coupled antiferromagnetically via their extended organic pillaring linkers.

Cited by 5 publications

References 76 publications

The Chemistry of Metal Organic Framework Materials

The Chemistry of Metal Organic Framework Materials

Spin-Resolved Band Structure of Hoffman Clathrate [Fe(pz)2Pt(CN)4] as an Essential Tool to Predict Optical Spectra of Metal–Organic Frameworks

Ground-State Spin Dynamics in d1 Kagome-Lattice Titanium Fluorides

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Product

Resources

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Spin-Resolved Band Structure of Hoffman Clathrate [Fe(pz)₂Pt(CN)₄] as an Essential Tool to Predict Optical Spectra of Metal–Organic Frameworks

Ground-State Spin Dynamics in d¹ Kagome-Lattice Titanium Fluorides