Verdazyl Radical, a  Building Block for a Six-Spin-Center 2p–3d–4f Single-Molecule Magnet

Novitchi, Ghénadie; Shova, Sergiu; Lan, Yanhua; Wernsdorfer, Wolfgang; Train, Cyrille

doi:10.1021/acs.inorgchem.6b02380

Cited by 46 publications

(30 citation statements)

References 42 publications

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“…The metal-radical heterospin strategy, in which metal ions link with stable organic radicals, is extremely fascinating for designing molecular magnetic materials [1][2][3][4][5][6]. Based on this kind of heterospin approach, 3d [7][8][9], 4f [10][11][12][13][14][15][16][17], and 3d-4f [18][19][20][21][22][23] compounds have been obtained so far by employing various organic radicals, such as N 2 3− [15,16], HAN 3− [24], TTF + [25], thiadiazoyl [14], and nitronyl nitroxide radical ligands [6,7,10,13,19,23,[26][27][28][29][30][31][32]. In particular, nitronyl nitroxide radicals are often used as building blocks to construct metal compounds with various topology structures due to the substituent groups of nitronyl nitroxides being able to effectively regulate the spatial arrangement of magnetic building blocks [33].…”

Section: Introductionmentioning

confidence: 99%

Two-Dimensional Nitronyl Nitroxide–Cu Networks Based on Multi-Dentate Nitronyl Nitroxides: Structures and Magnetic Properties

Xie

et al. 2021

Magnetochemistry

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Two multi-dentate nitronyl nitroxide radicals, namely, bisNITPhPy ([5-(4-pyridyl)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl)]benzene) and NIT-3Py-5-4Py (2-{3-[5-(4-pyridyl)]pyridyl}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), were assembled with CuII ions to obtain two-dimensional heterospin 2p–3d coordination polymers [Cu7(hfac)14(bisNITPhPy)2]n (1) and [Cu2(hfac)4(NIT-3Py-5-4Py)]n (2) (hfac: hexafluoroacetylacetonate). In both compounds, the bisNITPhPy and NIT-3Py-5-3Py radicals acted as pentadentate and tetradentate ligands, respectively, to connect with CuII ions, generating a 2D layer structure. The analysis of the magnetic behavior indicated that strong antiferromagnetic coupling and ferromagnetic interaction (J = 17.1 cm−1) coexisted in 1. For 2, there were ferromagnetic couplings between the CuII ion and NO group, as well as the CuII ion and radical via the pyridine ring with J1 = 32.8 and J2 = 2.2 cm−1, respectively.

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Section: Introductionmentioning

confidence: 99%

Two-Dimensional Nitronyl Nitroxide–Cu Networks Based on Multi-Dentate Nitronyl Nitroxides: Structures and Magnetic Properties

Xie

et al. 2021

Magnetochemistry

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“…Vaz et al have successfully synthesized a Co–Dy dinuclear compound through a dissymmetric compartmental ligand with the nitronyl nitroxide unit . Train and co-workers employ a verdazyl radical as the building block to obtain a six-spin-center 2p–3d–4f SMM . We have recently also focused on the preparation of 3d–4f compounds using paramagnetic nitronyl nitroxide ligands, and a series of discrete molecules, one- and two-dimensional (2D) d–f compounds, have been obtained .…”

Section: Introductionmentioning

confidence: 99%

Functionalized Nitronyl Nitroxide Biradicals for the Construction of 3d–4f Heterometallic Compounds

Sun

Yang

et al. 2018

Inorg. Chem.

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Functionalized nitronyl nitroxide biradical ligands incorporating pyridine groups hold Co and Ln ions together, creating biradical-based 3d-4f tetranuclear complexes [LnCo(hfac)(NITPhPybis)] [Ln = Gd (1), Tb (2), Dy (3), and Ho (4); NITPhPybis = 5-(4-pyridyl)-1,3-bis(1'-oxyl-3'-oxido-4',4',5',5'-tetramethyl-4,5-hydro-1 H-imidazol-2-yl)benzene; hfac = hexafluoroacetylacetonate]. These complexes have a centrosymmetric cyclic molecular structure in which two biradicals perform as tetradentate ligands to bind two Co and two Ln ions, resulting in a rare octaspin system. Direct-current (dc) magnetic susceptibility studies reveal that the strong antiferromagnetic Co-NO magnetic exchange dominates the present magnetic system, while magnetic coupling of Gd-ON is ferromagnetic. Analysis of the magnetic data of the Gd complex allows us to determine the magnetic parameters through the appropriate magnetic model. Alternating-current (ac) magnetic susceptibility investigations indicate that 2 displays frequency-dependent out-of-phase signals under a zero dc field, while ac magnetic susceptibilities of 3 show field-induced frequency dependence, which is a typical feature of slow relaxation of the magnetization. Complexes 1-4 represent the first nitronyl nitroxide biradical-based 3d-4f compounds.

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“…Such radicals are TEMPO nitronyl–nitroxide (Chart ), or verdazyl derivatives, which are functionalized with various coordinating groups. Almost all 2p–3d–4f complexes reported in the last years have been obtained following a one-pot procedure, by reacting the radical with 3d and 4f hexafluoroacetylacetonato complexes . The final architecture of the 2p–3d–4f complexes can be strongly influenced when the R groups in NitR coordinate through their donor atom(s) to one of the metal ions forming discrete complexes, − or coordination polymers. , The magnetic properties of all these complexes arise from the interplay of two exchange pathways: 2p–3d and 2p–4f.…”

Section: Introductionmentioning

confidence: 99%

SMM Behavior Tuned by an Exchange Coupling LEGO Approach for Chimeric Compounds: First 2p–3d–4f Heterotrispin Complexes with Different Metal Ions Bridged by One Aminoxyl Group

et al. 2019

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Coordination compounds containing three different spin carriers (2p, 3d, and 4f), with the general formula [M II Dy III (LH)-(hfac) 5 ] (M = Co, Ni, Mn, Zn), have been obtained using Mannich ligands decorated with a nitronyl−nitroxide fragment. The synthetic approach is general and leads to binuclear 3d−4f complexes, the two metal ions being bridged by one aminoxyl group and by one oxygen atom arising from a hfac − ligand. Triangular spin topology affords significant 2p−3d, 3d−4f, and 2p−4f exchange interactions. For the [Co II Dy III Rad] derivative obtained using a nitronyl−nitroxide chiral ligand, a high energy barrier (∼200 cm −1 ) and a slow relaxation behavior below 30 K were found and rationalized by ab initio calculations. The improvement of magnetic properties comes from the synergy of optimal single ions properties and exchange couplings contributions where the Co II −Rad interaction becomes the leading one. The role played by this interaction is clearly proved by the investigation of the magnetic properties of the [Zn II Dy III Rad] derivative, with a much lower energy barrier (12.7 cm −1 ) and by the lack of SMM behavior of the previously reported [Co II Dy III Rad] compound (Chem. Commun. 2017, 53, 6504), with a linear topology of spin carriers and a negligible Co II −Rad interaction.

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Verdazyl Radical, a Building Block for a Six-Spin-Center 2p–3d–4f Single-Molecule Magnet

Cited by 46 publications

References 42 publications

Two-Dimensional Nitronyl Nitroxide–Cu Networks Based on Multi-Dentate Nitronyl Nitroxides: Structures and Magnetic Properties

Two-Dimensional Nitronyl Nitroxide–Cu Networks Based on Multi-Dentate Nitronyl Nitroxides: Structures and Magnetic Properties

Functionalized Nitronyl Nitroxide Biradicals for the Construction of 3d–4f Heterometallic Compounds

SMM Behavior Tuned by an Exchange Coupling LEGO Approach for Chimeric Compounds: First 2p–3d–4f Heterotrispin Complexes with Different Metal Ions Bridged by One Aminoxyl Group

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