MnIII–FeIII Heterometallic Compounds within Hydrogen-Bonded Supramolecular Networks Promoted by an [Fe(CN)5(CNH)]2– Building Block: Structural and Magnetic Properties

Aguilà, David; Jeannin, Olivier; Fourmigué, Marc; Jeon, Ie‐Rang

doi:10.1021/acs.inorgchem.8b00983

Cited by 10 publications

(7 citation statements)

References 126 publications

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“…It is interesting to note that the 3D antiferromagnetic order of Co(BPDC)(IQNO) does not prevent the manifestation of chain dynamics. Such behavior has been only recently investigated in a small number of compounds. ,, To probe the influence of the applied dc magnetic field on the dynamics of the chain component, variable-frequency ac susceptibility measurements were performed at various applied fields below H dc = 500 Oe (Figure S8). As expected, the slowest dynamics were observed at H dc = 250 Oe, which is near the metamagnetic transition line observed in the magnetic phase diagram (Figure ).…”

Section: Resultsmentioning

confidence: 99%

Slow Magnetic Relaxation of Co(II) Single Chains Embedded within Metal–Organic Superstructures

et al. 2019

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Two coordination polymers of the type Co(BPDC)(N-ox), with BPDC being 4,4′-biphenyldicarboxylate and N-ox being pyridine N-oxide (PNO) or isoquinoline N-oxide (IQNO), have been synthesized and characterized. The compounds feature 2D and 3D metal–organic networks that encapsulate Co(II)-based chains in a rigid superstructure. The dc and ac magnetic properties of these Co(BPDC)(N-ox) materials have been investigated alongside those of a related Co(BDC)(PNO) compound (where BDC is 1,4-benzenedicarboxylate), which contains a smaller dicarboxylate linker. These Co(II)-containing coordination polymers exhibit slow magnetic relaxation, as observed by ac susceptibility measurements. The observed magnetic behavior of all compounds is consistent with an antiferromagnetic interaction between canted Co spins along the 1D skeleton, resulting in single-chain magnet behavior. In the case of Co(BPDC)(IQNO), weak interchain magnetic interactions yield 3D antiferromagnetic order while the inherent magnetic behavior stemming from the chain component is maintained. The combination of these effects in this material puts it at the frontier between single-chain magnets and classical bulk antiferromagnets. This work contributes to the limited group of materials featuring the organization of single-chain magnets within a coordination polymer superstructure.

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Section: Resultsmentioning

confidence: 99%

Slow Magnetic Relaxation of Co(II) Single Chains Embedded within Metal–Organic Superstructures

et al. 2019

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“…The one dimensional (1D) coordination heterobimetallic polymers comprising low spin orbitally degenerate cyano complexes are particularly infrequent. There are only a few magnetic molecular wires based on octahedral hexacyanidometallates of Fe III ( 3d 5 ) [ 23 , 24 , 25 , 26 ], Os III ( 5d 5 ) [ 16 ], and three—involving pentagonal bipyramidal (PBP) heptacyanidomolibdate(III) ( 4d 3 ) ( Scheme 1 a) [ 27 , 28 ].…”

Section: Introductionmentioning

confidence: 99%

Very Anisotropic 2D Molecular Magnetic Materials Based on Pentagonal Bipyramidal Heptacyanidorhenate(IV)

2022

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The first neutral 2D heterometallic assemblies based on orbitally degenerate heptacyanidorhenate(IV) were prepared and structurally characterized. An analysis of the magnetic data for the polycrystalline samples of Ph4P[{Mn(acacen)}2Re(CN)7]·Solv (1) and PPN[{Mn(acacen)}2Re(CN)7]·Solv (2) have shown that both materials display slow magnetic relaxation at temperatures below 10 and 21 K for 1 and 2, respectively. Despite the presence of the same molecular magnetic modules that make up the anionic layers, the studied 2D networks differ significantly in magnetic anisotropy, having a small coercive field (0.115 T) for 1 and a large one (~2.5 T) for 2 at 2 K. In addition, for both polymers a M(H) value does not saturate at the maximum available field of 7 T, and the material 2 is a metamagnet. This intriguing difference originates from the cooperative anisotropic spin interaction in ReIV−CN−MnIII pairs and the zero field splitting (ZFS) effect of MnIII ions with a noncollinear alignment of the local magnetic axes in crystals of the compounds.

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“…Octahedral hexacyanidoferrate(III) anion has been employed in many heterometallic chain compounds as a molecular linker between various spin carries [ 75 , 76 , 77 , 78 , 79 , 80 ]. First-order unquenched orbital momentum of the [Fe III (CN) 6 ] 3− complex results in strong magnetic anisotropy of spin chains, which is imposed by sufficiently high anisotropic exchange interactions in the Fe III -CN-M-CN linkages, the latter having been explored in detail both experimentally [ 81 , 82 ] and theoretically [ 78 , 79 , 80 ]. Several magnetic chain compounds containing related orbitally degenerate metalloligands [Mn III (CN) 6 ] 3− featuring slow magnetic relaxation were reported [ 83 , 84 , 85 ].…”

Section: Introductionmentioning

confidence: 99%

Interplay of Anisotropic Exchange Interactions and Single-Ion Anisotropy in Single-Chain Magnets Built from Ru/Os Cyanidometallates(III) and Mn(III) Complex

2023

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Two novel 1D heterobimetallic compounds {[MnIII(SB2+)MIII(CN)6]·4H2O}n (SB2+ = N,N’-ethylenebis(5-trimethylammoniomethylsalicylideneiminate) based on orbitally degenerate cyanidometallates [OsIII(CN)6]3− (1) and [RuIII(CN)6]3− (2) and MnIII Schiff base complex were synthesized and characterized structurally and magnetically. Their crystal structures consist of electrically neutral, well-isolated chains composed of alternating [MIII(CN)6]3- anions and square planar [MnIII(SB2+)]3+ cations bridged by cyanide groups. These -ion magnetic anisotropy of MnIII centers. These results indicate that the presence of compounds exhibit single-chain magnet (SCM) behavior with the energy barriers of Δτ1/kB = 73 K, Δτ2/kB = 41.5 K (1) and Δτ1/kB = 51 K, Δτ2 = 27 K (2). Blocking temperatures of TB = 2.8, 2.1 K and magnetic hysteresis with coercive fields (at 1.8 K) of 8000, 1600 Oe were found for 1 and 2, respectively. Theoretical analysis of the magnetic data reveals that their single-chain magnet behavior is a product of a complicated interplay of extremely anisotropic triaxial exchange interactions in MIII(4d/5d)–CN–MnIII fragments: −JxSMxSMnx−JySMySMny−JzSMzSMnz, with opposite sign of exchange parameters Jx = −22, Jy = +28, Jz = −26 cm−1 and Jx = −18, Jy = +20, Jz = −18 cm–1 in 1 and 2, respectively) and singleorbitally degenerate [OsIII(CN)6]3− and [RuIII(CN)6]3− spin units with unquenched orbital angular momentum in the chain compounds 1 and 2 leads to a peculiar regime of slow magnetic relaxation, which is beyond the scope of the conventional Glaubers’s 1D Ising model and anisotropic Heisenberg model.

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Mn^III–Fe^III Heterometallic Compounds within Hydrogen-Bonded Supramolecular Networks Promoted by an [Fe(CN)₅(CNH)]^2– Building Block: Structural and Magnetic Properties

Cited by 10 publications

References 126 publications

Slow Magnetic Relaxation of Co(II) Single Chains Embedded within Metal–Organic Superstructures

Slow Magnetic Relaxation of Co(II) Single Chains Embedded within Metal–Organic Superstructures

Very Anisotropic 2D Molecular Magnetic Materials Based on Pentagonal Bipyramidal Heptacyanidorhenate(IV)

Interplay of Anisotropic Exchange Interactions and Single-Ion Anisotropy in Single-Chain Magnets Built from Ru/Os Cyanidometallates(III) and Mn(III) Complex

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