Ferromagnetic Oxime-Based Manganese(III) Single-Molecule Magnets with Dimethylformamide and Pyridine as Terminal Ligands

Two new members of the [Mn6] family of single-molecule magnets (SMMs) of formulae [Mn6(μ3-O)2(H2N-sao)6(dmf)8](ClO4)2 (1) and [Mn6(μ3-O)2(H2N-sao)6(py)6(EtOH)2][ReO4]2·4EtOH (2), (dmf = N,N′-dimethylformamide, py = pyridine, H2N-saoH2 = salicylamidoxime) have been synthesized and characterized structurally and magnetically. Both compounds were straightforwardly prepared from the deprotonation of the H2N-saoH2 ligand in the presence of the desired manganese salt and solvent (dmf (1) vs. py (2)). Compound 1 crystallizes in the triclinic system with space group Pī and 2 crystallizes in the monoclinic system with space group P21/n. In the crystal packing of 1 and 2, the (ClO4)− (1) and [ReO4]− (2) anions sit between the cationic [Mn6]2+ units, which are H-bonded to –NH2 groups from the salicylamidoxime ligands. The study of the magnetic properties of 1 and 2 revealed ferromagnetic coupling between the MnIII metal ions and the occurrence of slow relaxation of the magnetization, which is a typical feature of single-molecule magnet behavior. The cationic nature of these [Mn6]2+ species suggests that they could be used as suitable building blocks for preparing new magnetic materials exhibiting additional functionalities.

Download Full-text

The localized electron: magnetic properties

10.1093/oso/9780198814597.003.0002 ◽

2018 ◽

Author(s):

Jean-Pierre Launay ◽

Michel Verdaguer

Keyword(s):

Single Molecule ◽

Model Systems ◽

Ferromagnetic Coupling ◽

Single Chain ◽

Single Molecule Magnets ◽

Magnetic Systems ◽

Orbital Interactions ◽

Prussian Blue Analogues ◽

Mononuclear Complexes

After preliminaries about electron properties, and definitions in magnetism, one treats the magnetism of mononuclear complexes, in particular spin cross-over, showing the role of cooperativity and the sensitivity to external perturbations. Orbital interactions and exchange interaction are explained in binuclear model systems, using orbital overlap and orthogonality concepts to explain antiferromagnetic or ferromagnetic coupling. The phenomenologically useful Spin Hamiltonian is defined. The concepts are then applied to extended molecular magnetic systems, leading to molecular magnetic materials of various dimensionalities exhibiting bulk ferro- or ferrimagnetism. An illustration is provided by Prussian Blue analogues. Magnetic anisotropy is introduced. It is shown that in some cases, a slow relaxation of magnetization arises and gives rise to appealing single-ion magnets, single-molecule magnets or single-chain magnets, a route to store information at the molecular level.

Download Full-text

New Silver(I) Coordination Polymer with Fe4 Single-Molecule Magnets as Long Spacer

Magnetochemistry ◽

10.3390/magnetochemistry4040043 ◽

2018 ◽

Vol 4 (4) ◽

pp. 43 ◽

Cited By ~ 1

Author(s):

Luca Rigamonti ◽

Manuela Vaccari ◽

Fabrizio Roncaglia ◽

Carlo Baschieri ◽

Alessandra Forni

Keyword(s):

Coordination Polymer ◽

Single Molecule ◽

Building Blocks ◽

Zero Field ◽

Single Molecule Magnets ◽

Long Distance ◽

Linear Arrangement ◽

Thermally Activated ◽

Supramolecular Architectures ◽

Donor Nitrogen

In continuation of our work on supramolecular architectures of single-molecule magnets (SMMs) as a promising strategy in developing their magnetic performance, in this paper we report the synthesis and single crystal X-ray structure of the centered triangular tetrairon(III) SMM, [Fe4(PhpPy)2(dpm)6], Fe4 (Hdpm = dipivaloylmethane, H3PhpPy = 2-(hydroxymethyl)-2-(4-(pyridine-4-yl)phenyl)propane-1,3-diol), and its assembly in the coordination polymer {[Fe4(PhpPy)2(dpm)6Ag](ClO4)}n, Fe4Ag, upon reaction with silver(I) perchlorate. Thanks to the presence of the pyridyl rings on the two tripodal ligands, Fe4 behaves as divergent ditopic linker, and due to the Fe4:AgClO4 1:1 ratio, Fe4Ag probably possesses a linear arrangement in which silver(I) ions are linearly coordinated by two nitrogen atoms, forming 1D chains whose positive charge is balanced by the perchlorate anions. The stabilization of such a polymeric structure can be ascribed to the long distance between the two donor nitrogen atoms (23.4 Å) and their donor power. Fe4Ag shows slow relaxation of the magnetization which follows a thermally activated process with Ueff/kB = 11.17(18) K, τ0 = 2.24(17) 10−7 s in zero field, and Ueff/kB = 14.49(5) K, τ0 = 3.88(8) 10−7 s in 1-kOe applied field, in line with what reported for tetrairon(III) SMMs acting as building blocks in polymeric structures.

Download Full-text

Cobalt(II) chloride adducts with acetonitrile, propan-2-ol and tetrahydrofuran: considerations on nuclearity, reactivity and synthetic applications

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229617000705 ◽

2017 ◽

Vol 73 (2) ◽

pp. 104-114 ◽

Cited By ~ 1

Author(s):

Danilo Stinghen ◽

André Luis Rüdiger ◽

Siddhartha O. K. Giese ◽

Giovana G. Nunes ◽

Jaísa F. Soares ◽

...

Keyword(s):

Single Molecule ◽

Building Blocks ◽

Direct Reaction ◽

X Ray Diffraction ◽

Single Molecule Magnets ◽

X Ray ◽

Ft Ir ◽

Bond Network ◽

Solvent Molecules ◽

Intramolecular Hydrogen

High-spin cobalt(II) complexes are considered useful building blocks for the synthesis of single-molecule magnets (SMM) because of their intrinsic magnetic anisotropy. In this work, three new cobalt(II) chloride adducts with labile ligands have been synthesized from anhydrous CoCl2, to be subsequently employed as starting materials for heterobimetallic compounds. The products were characterized by elemental, spectroscopic (EPR and FT–IR) and single-crystal X-ray diffraction analyses.trans-Tetrakis(acetonitrile-κN)bis(tetrahydrofuran-κO)cobalt(II) bis[(acetonitrile-κN)trichloridocobaltate(II)], [Co(C2H3N)4(C4H8O)2][CoCl3(C2H3N)]2, (1), comprises mononuclear ions and contains both acetonitrile and tetrahydrofuran (thf) ligands, The coordination polymercatena-poly[[tetrakis(propan-2-ol-κO)cobalt(II)]-μ-chlorido-[dichloridocobalt(II)]-μ-chlorido], [Co2Cl4(C3H8O)4], (2′), was prepared by direct reaction between anhydrous CoCl2and propan-2-ol in an attempt to rationalize the formation of the CoCl2–alcohol adduct (2), probably CoCl2(HOiPr)m. The binuclear complex di-μ-chlorido-1:2κ4Cl:Cl-dichlorido-2κ2Cl-tetrakis(tetrahydrofuran-1κO)dicobalt(II), [Co2Cl4(C4H8O)4], (3), was obtained from (2) after recrystallization from tetrahydrofuran. All three products present cobalt(II) centres in both octahedral and tetrahedral environments, the former usually less distorted than the latter, regardless of the nature of the neutral ligand. Product (2′) is stabilized by an intramolecular hydrogen-bond network that appears to favour atransarrangement of the chloride ligands in the octahedral moiety; this differs from thecisdisposition found in (3). The expected easy displacement of the bound solvent molecules from the metal coordination sphere makes the three compounds good candidates for suitable starting materials in a number of synthetic applications.

Download Full-text

Polysulfonylamine, XCVII [1] Di(organosulfonyl)amine und ihre konjugierten Anionen als simultane Baugruppen in zwei supramolekularen Strukturen / Polysulfonylamines, XCVII [1] Di(organosulfonyl)amines and their Conjugate Anions as Simultaneous Building Blocks in Two Supramolecular Structures

Zeitschrift für Naturforschung B ◽

10.1515/znb-1997-1014 ◽

1997 ◽

Vol 52 (10) ◽

pp. 1229-1236 ◽

Cited By ~ 2

Author(s):

Dagmar Henschel ◽

Karna Wijaya ◽

Oliver Moers ◽

Armand Blaschette ◽

Peter G. Jones

Keyword(s):

Crystal Packing ◽

Building Blocks ◽

Complex Compounds ◽

Monoclinic Space Group ◽

X Ray Diffraction ◽

Space Group ◽

Diffraction Structure ◽

Bond System ◽

Bond Network ◽

Anion Interaction

The complex compounds 4HN (SO2Me)2 · (diaza-18-crown-6) (1) and Na[N(SO2Ph)2] · 2HN(SO2Ph)2 · 2 (12-crown-4) · 2 MeOH (2) were obtained from their components and characterized by low-temperature X-ray diffraction. Structure 1 (monoclinic, space group P21/n) displays centrosymmetric formula units consisting of a biangular diazonia-18-crown-6 dication, two (MeSO2)2N− anions situated above and below the macrocycle and linked to the NH2+ groups via an N - H ··· O and N -H ··· N bond system, and finally two HN(SO2Me)2 molecules, each forming an N -H ··· O bond to one of the anions. The molecule-anion entity represents an iso form of the [(RSO2)2N -H ··· N (SO2R)2]− homoconjugates previously described. The crystal packing of 1 is stabilized by an extensive and highly organized [H2C -H ··· O(S)] hydrogen bond network. Structure 2 (monoclinic, space group P21/n) exhibits inconspicuous [Na(12-crown-4)2]+ cations and, as a striking feature, supramolecular anions assembled from a central (PhSO2)2N− ion, two MeOH molecules flanking the amide anion, and two HN (SO2Ph)2 molecules bonded to the MeOH moieties. The assembly is held together by two N -H ··· O(H )(Me) bonds, one MeO -H ··· N− bond and one MeO -H ··· O(anion) interaction. For both structures, conformational peculiarities of the N(SO2C)2 groups are discussed.

Download Full-text

A new Mo(iv) complex with the pentadentate (N3O2) Schiff-base ligand: the first non-cyanide pentagonal–bipyramidal paramagnetic 4d complex

Dalton Transactions ◽

10.1039/c7dt02912h ◽

2017 ◽

Vol 46 (41) ◽

pp. 14083-14087 ◽

Cited By ~ 6

Author(s):

V. S. Mironov ◽

T. A. Bazhenova ◽

Yu. V. Manakin ◽

K. A. Lyssenko ◽

A. D. Talantsev ◽

...

Keyword(s):

Schiff Base ◽

Single Molecule ◽

Schiff Base Ligand ◽

Schiff Base Complex ◽

Building Blocks ◽

Single Molecule Magnets ◽

Base Complex

Characterized both structurally and magnetically, a new molybdenum(iv) Schiff-base complex represents a novel family of the pentagonal–bipyramidal 4d-metal-based building blocks for construction of advanced single-molecule magnets.

Download Full-text

Magnetic properties of trinuclear nickel complexes-building blocks of single-molecule magnets

Russian Journal of Inorganic Chemistry ◽

10.1134/s0036023612030126 ◽

2012 ◽

Vol 57 (3) ◽

pp. 411-415

Author(s):

A. V. Klimov ◽

V. L. Berdinskii

Keyword(s):

Magnetic Properties ◽

Single Molecule ◽

Nickel Complexes ◽

Building Blocks ◽

Single Molecule Magnets

Download Full-text

Crystal packing effects within [MnIII3O]7+ single-molecule magnets: Controlling intermolecular antiferromagnetic interactions

Polyhedron ◽

10.1016/j.poly.2011.05.030 ◽

2011 ◽

Vol 30 (18) ◽

pp. 3272-3278 ◽

Cited By ~ 6

Author(s):

Chen-I Yang ◽

Kai-Hung Cheng ◽

Shao-Po Hung ◽

Motohiro Nakano ◽

Hui-Lien Tsai

Keyword(s):

Single Molecule ◽

Crystal Packing ◽

Single Molecule Magnets ◽

Crystal Packing Effects ◽

Packing Effects

Download Full-text

Crystal Structure, Spectroscopic and Thermal Investigations of a New 4-Ammonio-2,2,6,6-tetramethylpiperidinium Tetrachlorozincate(II)

E-Journal of Chemistry ◽

10.1155/2010/962121 ◽

2010 ◽

Vol 7 (4) ◽

pp. 1562-1570 ◽

Cited By ~ 1

Author(s):

M. El Glaoui ◽

M. L. Mrad ◽

E. Jeanneau ◽

C. Nasr

Keyword(s):

Crystal Structure ◽

Hydrogen Bonds ◽

Crystal Packing ◽

Monoclinic System ◽

Space Group ◽

Cell Parameters ◽

Open Framework ◽

Atomic Arrangement ◽

Thermal Investigations ◽

Physicochemical Studies

The new complex of Zn(II) with 4-ammino-2,2,6,6-tetramethylpiperidine, [C9H22N2]ZnCl4, has been prepared and characterized by various physicochemical studies. This compound crystallizes in the monoclinic system, with the space group P21/c and the following cell parameters: a = 9.8682(7), b = 7.5164(5), c = 21.019(2) Å, β = 99.003 (7)°, V = 1539.8(2) Å3and Z = 4. The crystal structure was solved and refined to R = 0.024 using 3070 reflections. The atomic arrangement can be described by slightly distorted tetrahedral ZnCl42-anions and 4-ammmonio-2,2,6,6-tetramethylpiperidinium cations holding together by different interactions. The four chlorine atoms of the ZnCl42-tetrahedron are acting as acceptors of hydrogen bonds. The crystal packing is influenced by cation-to-anion N-H…Cl and C-H…Cl hydrogen bonds leading to open framework architecture.

Download Full-text

Homochiral Ferromagnetic Coupling Dy2 Single-Molecule Magnets with Strong Magneto-Optical Faraday Effects at Room Temperature

Inorganic Chemistry ◽

10.1021/acs.inorgchem.1c01218 ◽

2021 ◽

Author(s):

Cai-Ming Liu ◽

Rong Sun ◽

Bing-Wu Wang ◽

Fan Wu ◽

Xiang Hao ◽

...

Keyword(s):

Single Molecule ◽

Room Temperature ◽

Ferromagnetic Coupling ◽

Single Molecule Magnets ◽

Faraday Effects

Download Full-text

Is [ReCl4(CN)2]2− a good Building Block for Single Molecule Magnets? A Theoretical Investigation.

10.26434/chemrxiv-2022-jwc57 ◽

2022 ◽

Author(s):

Christoph van Wüllen ◽

Eva M. V. Kessler

Keyword(s):

Single Molecule ◽

Building Blocks ◽

Ligand Field ◽

Zero Field ◽

Spin Orbit ◽

Computational Results ◽

Zero Field Splitting ◽

Single Molecule Magnets ◽

Field Splitting ◽

Orbit Perturbation

Building blocks containing $5d$ spin centres are promising for constructing single molecule magnets due to their large spin-orbit interaction, but experimental and computational results obtained so far indicate that this might not be the case for Re$^\textrm{IV}$ centres in an octahedral environment. Density functional results obtained in this work for [ReCl$_4$(CN)$_2$]$^{2-}$ and trinuclear complexes formed by attaching Mn$^\textrm{II}$ centres to the cyano ligands indicate that zero field splitting in such complexes exhibits large rhombicity (which leads to fast relaxation of the magnetisation) even if there are only small distortions from an ideal geometry with a four-fold symmetry axis. This is already apparent if second-order spin-orbit perturbation theory is applied but even more pronounced if higher-order spin-orbit effects are included as well, as demonstrated by wavefunction based calculations. Computational results are cast into a ligand field model and these simulations show that especially a distortion which is not along the $C_4/C_2$ axeshas a large effect on the rhombicity. Quantum simulations on these complexes are difficult because the zero field splitting strongly depends on the energetic position of the low-lying doublets from the $t_{2g}^3$ configuration.

Download Full-text