Magnetism in one-dimensional metal–nitronyl nitroxide radical system

Meng, Xixi; Shi, Wei

doi:10.1016/j.ccr.2018.02.002

Cited by 103 publications

(45 citation statements)

References 141 publications

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“…[1] These onedimensional structures exhibit magnetic bistability at the molecular level thanks to the strong anisotropy of their spin carriers,t heir strong intramolecular magnetic exchange and good magnetic insulation. [2] Among them, chains made of nitronyl-nitroxide (NIT) organic radicals [3] and 3d [4] or 4f [5] ions show significant SCM behavior.…”

Section: Single-chainmagnets(scm)areone-dimensionalanaloguesmentioning

confidence: 99%

“…Its aromatic group ensures the chain robustness (intra-chain p-stacking interactions) and is connected in para to an aliphatic tail (Supporting Informa-tion, Figure S1, Table S1). This latter possesses large degrees of freedom targeted to give rise to large crystallographic asymmetric unit because of the huge variety of structural conformations that it could accommodate.The stoichiometric reaction of NIT-O-hexyl with the [Tb(hfac) 3 (Tables S2-S3). The asymmetric unit is made of two and ah alf radicals and two and ah alf terbium atoms (Tb1, Tb2, Tb3) that alternate ( Figure 1).…”

Section: Single-chainmagnets(scm)areone-dimensionalanaloguesmentioning

confidence: 99%

“…Shortest Tb-Tb distance is 8.39 . TheN IT-4fc hains [3] can be described by the Cx-Ln-Cx angle where Cx is the central Ca tom of the tetramethylimidazoline group.U sually,t wo consecutive angles compensate along the chain direction to give rise to aregular and flat zigzag chain. [7] In TbNIT-Ph-O-Hexyl,t he picture is very different.…”

Section: Single-chainmagnets(scm)areone-dimensionalanaloguesmentioning

confidence: 99%

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Chiral Supramolecular Nanotubes of Single‐Chain Magnets

et al. 2019

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We report a single‐chain magnet (SCM) made of a terbium(III) building block and a nitronyl‐nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long‐range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self‐organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44 % porosity. Ab initio calculations highlight that each TbIII ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite‐size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (Hc=2400 Oe MR=2.09 μB at 0.5 K) for this class of compounds.

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Section: Single-chainmagnets(scm)areone-dimensionalanaloguesmentioning

confidence: 99%

Section: Single-chainmagnets(scm)areone-dimensionalanaloguesmentioning

confidence: 99%

Section: Single-chainmagnets(scm)areone-dimensionalanaloguesmentioning

confidence: 99%

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Chiral Supramolecular Nanotubes of Single‐Chain Magnets

et al. 2019

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“…The NIT‐4f chains can be described by the Cx‐Ln‐Cx angle where Cx is the central C atom of the tetramethylimidazoline group. Usually, two consecutive angles compensate along the chain direction to give rise to a regular and flat zig‐zag chain .…”

Section: Figurementioning

confidence: 99%

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

et al. 2019

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“…Organic radical species can also be applied to spin sources [ 6 , 7 , 8 ], and ligands can serve not only as a cap, bridge, or polyhedron regulator, but also as a spin carrier. According to the “metal–radical approach” proposed by Gatteschi et al [ 15 , 16 ], direct metal-radical coordination bonds afford considerable magnetic exchange interaction. A number of ligands based on 2-azaaryl tert -butyl nitroxides (aminoxyls) have been explored for 2p-3d [ 17 , 18 , 19 , 20 , 21 , 22 , 23 ] as well as 2p-4f heterospin systems [ 24 , 25 , 26 , 27 , 28 ].…”

Section: Introductionmentioning

confidence: 99%

A Hidden Coordination-Bond Torsional Deformation as a Sign of Possible Spin Transition in Nickel(II)-Bis(nitroxide) Compounds

Kyoden

Ishida

2020

Molecules

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Complex formation of nickel(II) tetrafluoroborate and tert-butyl 5-phenyl-2-pyridyl nitroxide (phpyNO) in the presence of sodium cyanate gave a discrete molecule [Ni(phpyNO)2(X)2] (X = NCO). The Ni-O-N-Csp2 torsion angles were reduced on heating; 33.5(5)° and 36.2(4)° at 100 K vs. 25.7(10)° and 32.3(11)° at 400 K. The magnetic behavior was almost diamagnetic below ca. 100 K, and the χmT value reached 1.04 cm3 K mol−1 at 400 K. An analysis using the van’t Hoff equation indicates a possible spin transition at T1/2 >> 400 K. Density functional theory calculation shows that the singlet-quintet energy gap decreases as the structural change from 100 to 400 K. The geometry optimization results suggest that the diamagnetic state has the Ni-O-N-Csp2 torsion angles of 32.7° while the Stotal = 2 state has those of 11.9°. The latter could not be experimentally observed even at 400 K. After overviewing the results on the known X = Br, Cl, and NCS derivatives, the magnetic behavior is described in a common phase diagram. The Br and Cl compounds undergo the energy level crossing of the high-/low-spin states, but the NCS and NCO compounds do not in a conventional experimental temperature range. The spin transition mechanism in this series involves the exchange coupling switch between ferro- and antiferromagnetic interactions, corresponding to the high- and low-spin phases, respectively.

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Magnetism in one-dimensional metal–nitronyl nitroxide radical system

Cited by 103 publications

References 141 publications

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

A Hidden Coordination-Bond Torsional Deformation as a Sign of Possible Spin Transition in Nickel(II)-Bis(nitroxide) Compounds

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