Exploiting Host-Guest Chemistry to Manipulate Magnetic Interactions in Metallosupramolecular M4L6 Tetrahedral Cages

Reaction of Ni(OTf)2 with the bisbidentate quaterpyridine ligand L results in the self-assembly of a tetrahedral, paramagnetic cage [NiII4L6]8+. By selectively exchanging the bound triflate from [OTfÌNiII4L6](OTf)7 (1), we have been able to prepare a series of host-guest complexes that feature an encapsulated paramagnetic tetrahalometallate ion inside this paramagnetic host giving [MIIX4ÌNiII4L6](OTf)6, where MIIX42− = MnCl42− (2), CoCl42− (5), CoBr42− (6), NiCl42− (7), CuBr42− (8) or [MIIIX4ÌNiII4L6](OTf)7, where MIIIX4− = FeCl4− (3), FeBr4− (4). Triflate-to-tetrahalometallate exchange occurs in solution and can also be accomplished through single-crystal-to-single-crystal transformations. Host-guest complexes 1-8 all crystallise as homochiral racemates in monoclinic space groups, wherein the four {NiN6} vertex within a single Ni4L6 unit possess the same Δ or Λ stereochemistry. Magnetic susceptibility and magnetisation data show that the magnetic exchange between metal ions in the host [NiII4] complex, and between the host and the MX4n- guest, are of comparable magnitude and antiferromagnetic in nature. Theoretically derived values for the magnetic exchange are in close agreement with experiment, revealing that large spin densities on the electronegative X-atoms of particular {MX4}n− guest molecules leads to stronger host-guest magnetic exchange interactions.

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Exploiting host–guest chemistry to manipulate magnetic interactions in metallosupramolecular M4L6 tetrahedral cages

Chemical Science ◽

10.1039/d1sc00647a ◽

2021 ◽

Vol 12 (14) ◽

pp. 5134-5142 ◽

Cited By ~ 1

Author(s):

Aaron J. Scott ◽

Julia Vallejo ◽

Arup Sarkar ◽

Lucy Smythe ◽

E. Regincós Martí ◽

...

Keyword(s):

Exchange Interactions ◽

Magnetic Interactions ◽

Magnetic Exchange ◽

Guest Chemistry

The tetrahedral [NiII4L6]8+ cage can reversibly bind paramagnetic MX41/2− guests, inducing magnetic exchange interactions between host and guest.

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Structural and Magnetic Properties of Mn-Based Diluted Magnetic Semiconductors and Alloys

Research Letters in Physics ◽

10.1155/2009/406095 ◽

2009 ◽

Vol 2009 ◽

pp. 1-4 ◽

Cited By ~ 1

Author(s):

A. Alsaad

Keyword(s):

Rock Salt ◽

Diluted Magnetic Semiconductors ◽

Magnetic Semiconductors ◽

Exchange Interactions ◽

Magnetic Interactions ◽

Local Spin Density Approximation ◽

Energy Minimum ◽

Rock Salt Structure ◽

Magnetic Exchange ◽

Salt Structure

Direct supercell approach calculations of the magnetic exchange interactions in Mn-doped ScN was carried out in the local spin density approximation by using the muffin-tin-orbital Green's function method. We found that magnetic interactions are long range interactions and affected by the randomness, band gap corrections, and carrier concentrations. Using total energy minimization approach we found that the global energy minimum of MnN is obtained for zinc-blende structure. If the compound is compressed by 6%, the energy minimum corresponds to the rock-salt structure in disagreement with the experimentally observed tetragonal distorted rock-salt structure, known as -phase. An isostructural phase transition for alloys from MnN -phase to -ScN phase was found to occur at a hydrostatic pressure of 18 GPa. We predict above room temperature for Mn concentrations of about 10% in ScN : Mn system.

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Isotropic and Anisotropic Magnetic Exchange Interactions through .mu.-N1,N2 1,2,4-Triazole and .mu.-Sulfato Bridges: X-ray Crystal Structure, Magnetic Properties, and Single-Crystal EPR Study of (.mu.-4-Amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole-N',N1,N2,N'')(.mu.-sulfato-O,O')[(sulfato-O)aquacopper(II)]triaquacopper(II) Hydrate

Inorganic Chemistry ◽

10.1021/ic00125a015 ◽

1995 ◽

Vol 34 (21) ◽

pp. 5175-5182 ◽

Cited By ~ 61

Author(s):

Petra J. van Koningsbruggen ◽

Dante Gatteschi ◽

Rudolf A. G. de Graaff ◽

Jaap G. Haasnoot ◽

Jan Reedijk ◽

...

Keyword(s):

Crystal Structure ◽

Magnetic Properties ◽

Single Crystal ◽

Exchange Interactions ◽

Magnetic Exchange ◽

X Ray

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Effects of substitution, solvent andpH on magnetic exchange interactions in SOD model systems: ESR, electrochemical and single crystal x-ray studies

Journal of Chemical Sciences ◽

10.1007/bf02870074 ◽

1996 ◽

Vol 108 (3) ◽

pp. 307-307

Author(s):

P S Subramanian ◽

D Srinivas ◽

Mohan M Bhadbhade ◽

M Velayuthum ◽

S Subramanian

Keyword(s):

Single Crystal ◽

Exchange Interactions ◽

Model Systems ◽

Magnetic Exchange ◽

X Ray

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Single-crystal studies of the zero-field splitting and magnetic exchange interactions in the magnetic susceptibility calibrant mercury cobalt-thiocyanate (HgCo(NCS)4)

Inorganic Chemistry ◽

10.1021/ic00054a012 ◽

1993 ◽

Vol 32 (2) ◽

pp. 182-188 ◽

Cited By ~ 56

Author(s):

David Nelson ◽

Leonard W. Ter Haar

Keyword(s):

Magnetic Susceptibility ◽

Single Crystal ◽

Exchange Interactions ◽

Zero Field ◽

Zero Field Splitting ◽

Magnetic Exchange ◽

Field Splitting

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Single-Crystal EPR and X-Ray Studies of Magnetic Exchange Interactions and the Molecular Structure of Dipropylenetriamineethylenediaminecopper(II) Perchlorate, [Cu(dpt)(en)](ClO4)2

Inorganic Chemistry ◽

10.1021/ic980071n ◽

1998 ◽

Vol 37 (23) ◽

pp. 5983-5991 ◽

Cited By ~ 14

Author(s):

Murugesan Velayutham ◽

Babu Varghese ◽

Sankaran Subramanian

Keyword(s):

Molecular Structure ◽

Single Crystal ◽

Exchange Interactions ◽

Magnetic Exchange ◽

X Ray

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Determining the range of magnetic interactions from the relations between magnon eigenvalues at high-symmetry k points

10.21203/rs.3.rs-334283/v1 ◽

2021 ◽

Author(s):

Di Wang ◽

Jihai Yu ◽

Feng Tang ◽

Yuan Li ◽

Xiangang Wan

Keyword(s):

Magnetic Moments ◽

A Priori ◽

Exchange Interactions ◽

Wave Theory ◽

Real Space ◽

Simple Relation ◽

Magnetic Interactions ◽

High Symmetry ◽

Magnetic Exchange ◽

The Fourier Transform

Abstract Magnetic exchange interactions (MEIs) define networks of coupled magnetic moments and lead to a surprisingly rich variety of their magnetic properties. Typically MEIs can be estimated by fitting experimental results. But how many MEIs need to be included in the fitting process for a material is not clear a priori, which limits the quality of results obtained by these conventional methods. In this paper, based on linear spin-wave theory but without performing matrix diagonalization, we show that for a general quadratic spin Hamiltonian, there is a simple relation between the Fourier transform of MEIs and the sum of square of magnon energies (SSME). We further show that according to the real-space distance range within which MEIs are considered relevant, one can obtain the corresponding relationships between SSME in momentum space. We also develop a theoretical tool for tabulating the rule about SSME. By directly utilizing these characteristics and the experimental magnon energies at only a few high-symmetry k points in the Brillouin zone, one can obtain strong constraints about the range of exchange path beyond which MEIs can be safely neglected. Our methodology is also general applicable for other Hamiltonian with quadratic Fermi or Boson operators.

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Different Polyoxometalate Structures Obtained from the Na11H[H(2-x)Bi2W20O70(HWO3)x]·46H2O(x=1.4).

JORDANIAN JOURNAL OF ENGINEERING AND CHEMICAL INDUSTRIES (JJECI) ◽

10.48103/jjeci162018 ◽

2018 ◽

Vol 1 (2) ◽

pp. 93-100

Author(s):

Suhair Atta

Keyword(s):

Single Crystal ◽

Self Assembly ◽

Multiple Testing ◽

X Ray Diffraction ◽

Triclinic Space Group ◽

X Ray ◽

Space Groups ◽

Cell Parameters ◽

New Family ◽

Ft Ir

In the supramolecular chemistry world, Polyoxometalates (POMs) are considered as a new family of inorganic molecular containers, construct itself by self-assembly reaction from very small units, to form a cluster with unique structural and properties. three structures reported in this paper - differ in their unit cell parameters and also differ from the well-known - as the result of reaction of the Na11H[H(2- x)Bi2W20O70(HWO3)x]·46H2O (x=1.4) with Ca ion at different pH conditions. These structures are [Ca(H2O)7]2[Na(H2O)2]2[HBi2W20O70(HWO3)].14H2O(1), H2[NH4]10[HBi2W20O70(HWO3)] (2), and [NH4]6[Na(H2O)4]2[Ca(H2O)4]2[W12O42].2H2O (3). The last one is bismuth-free and it is formed through reassembly of the precursor. Full structural characterization was made by multiple testing techniques such as single-crystal X-ray diffraction, UV-visible spectroscopy, FT-IR, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). The single-crystal X-ray diffraction results for the three compounds are as follows:(1), Triclinic, space group P-1, while (2) and (3) crystallize in monoclinic space groups C2/m and P21/n respectively.

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Determination of the Range of Magnetic Interactions from the Relations between Magnon Eigenvalues at High-Symmetry κ Points

Chinese Physics Letters ◽

10.1088/0256-307x/38/11/117101 ◽

2021 ◽

Vol 38 (11) ◽

pp. 117101

Author(s):

Di Wang ◽

Jihai Yu ◽

Feng Tang ◽

Yuan Li ◽

Xiangang Wan

Keyword(s):

Magnetic Moments ◽

A Priori ◽

Exchange Interactions ◽

Wave Theory ◽

Real Space ◽

Simple Relation ◽

Magnetic Interactions ◽

High Symmetry ◽

Magnetic Exchange ◽

The Fourier Transform

Magnetic exchange interactions (MEIs) define networks of coupled magnetic moments and lead to a surprisingly rich variety of their magnetic properties. Typically MEIs can be estimated by fitting experimental results. Unfortunately, how many MEIs need to be included in the fitting process for a material is unclear a priori, which limits the results obtained by these conventional methods. Based on linear spin-wave theory but without performing matrix diagonalization, we show that for a general quadratic spin Hamiltonian, there is a simple relation between the Fourier transform of MEIs and the sum of square of magnon energies (SSME). We further show that according to the real-space distance range within which MEIs are considered relevant, one can obtain the corresponding relationships between SSME in momentum space. By directly utilizing these characteristics and the experimental magnon energies at only a few high-symmetry k points in the Brillouin zone, one can obtain strong constraints about the range of exchange path beyond which MEIs can be safely neglected. Our methodology is also generally applicable for other Hamiltonian with quadratic Fermi or Boson operators.

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