Functionalized nitronyl nitroxide biradical bridged one-dimensional lanthanide chains: slow magnetic relaxation in the Tb and Dy analogues

Li, Hongdao; Sun, Juan; Yang, Meng; Sun, Zan; Xie, Jing; Ma, Yue; Li, Licun

doi:10.1039/c7nj02006f

Cited by 26 publications

(20 citation statements)

References 64 publications

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“…In complex 1, the bond lengths of the two Gd1-O rad bonds are 2.383(8) Å and 2.472(7) Å, respectively, and the distance of Gd2-O rad is 2.454(7) Å. The bond lengths here are consistent with those existed in other nitronyl nitroxide biradical-Gd III complexes [26][27][28]. The length of the Gd-O hfac bond ranges from 2.343(9) to 2.412(7) Å.…”

Section: Synthetic Aspect and Crystal Structuressupporting

confidence: 82%

“…Nitronyl nitroxide biradical-Ln strategy provides new chances for designing molecular nanomagnets. Until now, only a handful of nitronyl nitroxide biradical-Ln compounds with slow relaxation of magnetization have been reported [25][26][27][28] due to the inherent difficulties encountered during the biradical preparation [30,31]. Very recently, we reported a series of nitronyl nitroxide biradical bridged tetranuclear lanthanide Crystallographic study proves that complexes 1-3 are isomorphous (Figures 1 and S3-S4) and all belong to the triclinic Pī system.…”

Section: Introductionmentioning

confidence: 89%

“…In 2018, K. R. Dunbar et al, reported the first metallacycle [Dy 3 (hfac) 6 (bptz −• ) 3 ](bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine; hfac = hexafluoroacetylacetonate) exhibiting temperature-dependent out-of-phase (χ") signals in the high-frequency range [15]. Noticeable, most of radical-Ln based molecular nanomagnets are constructed using mono-radicals [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22], and the employments of biradicals are less common [23][24][25][26][27][28]. Nitronyl nitroxide biradical-Ln approach, one hand, can result in interesting spin topology in which the unique magnetic behavior could be observed.…”

Section: Introductionmentioning

confidence: 99%

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Nitronyl Nitroxide Biradical-Based Binuclear Lanthanide Complexes: Structure and Magnetic Properties

et al. 2020

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Employing a new nitronyl nitroxide biradical NITPhPzbis(NITPhPzbis = 5-(1-pyrazolyl)-1,3-bis(1’-oxyl-3’-oxido-4’,4’,5’,5’-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene), a series of 2p-4f complexes [Ln2(hfac)6(H2O)(NITPhPzbis)] (LnIII = Gd1, Tb2, Dy3; hfac = hexafluoroacetylacetonate) were successfully synthesized. In complexes 1–3, the designed biradical NITPhPzbis coordinates with two LnIII ions in chelating and bridging modes to form a four-spin binuclear structure. Direct-current magnetic study of Gd analogue indicates that ferromagnetic exchange exists between the Gd ion and the radical while antiferromagnetic coupling dominates between two mono-radicals. Dynamic magnetic data show that the χ” signals of complex 3 exhibit frequency dependence under zero field, demonstrating slow magnetic relaxation behavior in complex 3. And the estimated values of Ueff and τ0 are about 8.4 K and 9.1 × 10−8 s, respectively.

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Section: Synthetic Aspect and Crystal Structuressupporting

confidence: 82%

Section: Introductionmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

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Nitronyl Nitroxide Biradical-Based Binuclear Lanthanide Complexes: Structure and Magnetic Properties

et al. 2020

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“…Crystal structures of related complexes involving lanthanide ions have been reported with acac ligands (Berg & Acosta, 1968;Binnemans, 2005;Filotti et al, 1996;Fujinaga et al, 1981 Katagiri et al, 2007;Li et al, 2017;Lim et al, 1996;Nakamura et al, 1986;Yan et al, 2009) and with hfa complexes (Subhan et al, 2014;Fratini et al, 2008;Hasegawa et al, 2013Kataoka et al, 2016;Rybkin et al, 2011;Tsaryuk et al, 2017;Wang et al, 2017;Yuasa et al, 2011).…”

Section: Database Surveymentioning

confidence: 99%

Structure of triaquatris(1,1,1-trifluoro-4-oxopentan-2-olato)cerium(III) as a possible fluorescent compound

Koizumi¹,

Hasegawa²,

Itadani³

et al. 2018

Acta Cryst E

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Luminescence due to the d-f transition of Ce 3+ is quite rare in metal-organic complexes where concentrate quenching frequently occurs. One of the possible ways to avoid this is to design an architecture with elongated metal-metal distances. In the structure of the title complex, triaquatris(1,1,1-trifluoro-4-oxopentan-2-olato-complex is linked to neighbouring ones by hydrogen bonding. Within the complex, the Ce III atom is coordinated by nine O atoms from three 1,1,1-trifluoro-4-oxopentan-2-olate (tfa) anions as bidentate ligands and three water molecules as monodentate ligands. Thus, the coordination number of Ce III atom is nine in a monocapped square-antiprismatic polyhedron. The F atoms of all three independent CF 3 groups in tfa are disordered over two positions with occupancy ratios of about 0.8:0.2. The intermolecular hydrogen bonds between the ligands involve tfa-water interactions along the [110] and [110] directions, generating an overall two-dimensional layered network structure. The presence of the F atoms in the tfa anion is responsible for an increased intermolecular metal-metal distance compared to that in the analogous acetylacetonate (acac) derivatives. Fluorescence from Ce 3+ is, however, not observed.

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“…Among which, since their magnetic coupling nature between neighboring paramagnetic metal centers through the cyanogroup and the molecular topological structures can be relatively easily predicted and controlled, the cyanide-bridged magnetic systems have been widely and intensely studied. Recently, with the aim not only of further disclosing the magneto-structure correlation but also more importantly for the great potential in many high-tech fields, a large numberof molecular magnetic materials containing a cyanide linkagewith different structural types have been synthesized and magnetically studied.Many of the reported cyanide-bridged magnetic assemblies showed very interesting magnetic properties [5,6,7,8,9,10,11,12,13,14] including single-molecule magnet (SMM) and single-chain magnet (SCM), which behave as nanosized magnets under the blocking temperature because of the energy barrierscoming from the large ground spin state (ST) and the strong easy axial anisotropy (D) [15,16,17].…”

Section: Introductionmentioning

confidence: 99%

Various Structural Types of Cyanide-Bridged FeIII–MnIII Bimetallic Coordination Polymers (CPs) and Polynuclear Clusters Based-on A New mer-Tricyanoiron(III)Building Block: Synthesis, Crystal Structures, and Magnetic Properties

et al. 2019

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Four cyanide-bridged FeIII–MnIII complexes {[Fe(qxcq)(CN)3][Mn(L1)(H2O)]}[Mn(L1)(H2O)(CH3OH)](ClO4)·1.5MeOH·0.5H2O (L1 = N,N′-bis(3-methoxy-5-bromosalicylideneiminate) (2), {[Fe(qxcq)(CN)3][Mn(L2)]}2·0.5H2O (L2 = N,N′-ethylene-bis(3-ethoxysalicylideneiminate)) (3), [Fe(qxcq)(CN)3][Mn(L3)] (L3 = bis(acetylacetonato)ethylenediimine) (4), [Fe(qxcq)(CN)3][Mn(L4)]·1.5MeOH·0.5CH3CN·0.25H2O (L4 = N,N′-(1,1,2,2-tetramethylethylene)bis(salicylideneiminate)) (5), were prepared by assembling a new structurally characterized mer-tricyanoiron(III) molecular precursor (Ph4P)[Fe(qxcq)(CN)3]·0.5H2O (qxcq− = 8-(2-quinoxaline-2-carboxamido)quinoline anion) (1) and the corresponding manganese(III) Schiff base compound. Complexes 2and 3containa cyanide-bridged heterobimetallic dinuclear entity, which can be further dimerized by self-complementary H-bond interactions through the coordinated water molecule from one complex and the free O4unit from the adjacent complex. Complexes 4 and 5 area one-dimensional coordination polymer (CP) comprised of the repeated [Mn(Schiffbase)-Fe(qxcq)(CN)3] units. Complex 4 shows a linear-chain conformation with two trans-located cyano groups bridgingthe neighboring Mn units, while complex 5 is a zigzag-like 1D CP, where the two cyano groups in cis configurationfunction as bridges. In bothcomplexes 4 and 5, the inter-chain π–πstack interactions within the aromaticrings of cyanide precursor extend the 1D chain into the supermolecular 2D networks. The magnetic property has been experimentally studied and theoretically fitted over the four Fe(III)-Mn(III) complexes, revealing the antiferromagnetic interaction in complexes 2 and 4 and the unusual ferromagnetic coupling in complexes 3 and 5 between the Fe(III) ion and the Mn(III) ion bridged by the cyano group. Furthermore, the different magnetic coupling nature has been analyzed on the basis of the magneto-structure correlation of the mer-tricyanometallate-based Fe(III)-Mn(III) magnetic system.

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Functionalized nitronyl nitroxide biradical bridged one-dimensional lanthanide chains: slow magnetic relaxation in the Tb and Dy analogues

Abstract: The first examples of Ln-nitronyl nitroxide 1D chains based on the functionalized nitronyl nitroxide biradical have been obtained, and complexes Dy and Tb exhibit slow magnetic relaxation behavior.

Cited by 26 publications

References 64 publications

Nitronyl Nitroxide Biradical-Based Binuclear Lanthanide Complexes: Structure and Magnetic Properties

Nitronyl Nitroxide Biradical-Based Binuclear Lanthanide Complexes: Structure and Magnetic Properties

Structure of triaquatris(1,1,1-trifluoro-4-oxopentan-2-olato)cerium(III) as a possible fluorescent compound

Various Structural Types of Cyanide-Bridged FeIII–MnIII Bimetallic Coordination Polymers (CPs) and Polynuclear Clusters Based-on A New mer-Tricyanoiron(III)Building Block: Synthesis, Crystal Structures, and Magnetic Properties

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