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Influence of a Lanthanide Ion on the Ni Site of a Heterobimetallic 3d-4f Mabiq Complex.

ABSTRACT: This work presents the synthesis and characterization of a 3d-4f bimetallic complex based on the redox-active macrocyclic biquinazoline ligand, Mabiq. The mixed Yb-Ni complex, [(Cp*)₂Yb(Mabiq)Ni]BArF (3), was synthesized upon reaction of [Ni^II(Mabiq)]BArF (2) with (Cp*)₂Yb^II(OEt₂). The molecular structures of 3 and its sister complex, [(Cp*)₂Yb(Mabiq)Ni][(Cp*)₂Yb(OTf)₂] (1), confirmed the presence of a Yb(III) center and a reduced Ni-Mabiq unit. Spectroscopy (absorption and NMR), cyclic voltammetry, and magnetic susceptibility studies were employed to analyze the electronic structure of 3, which is best described by the [(Cp*)₂Yb^III(Mabiq^•)Ni^II]⁺ formulation. Notably, the ligand-centered radical is delocalized over both the diketiminate and bipyrimidine units of the Mabiq ligand. The magnetic susceptibility and variable temperature NMR studies for 3 denote coupling between the Ni-Mabiq site and the peripheral Yb center-previously unobserved in 3d-3d Mabiq complexes. The complex nature of the exchange interactions is highlighted by the multiconfigurational ground state for 3, comprising nearly degenerate singlet and triplet states.

SUBMITTER: Boyce SAJ

PROVIDER: S-EPMC7116554 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

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Influence of a Lanthanide Ion on the Ni Site of a Heterobimetallic 3d-4f Mabiq Complex.

Boyce Stuart A J SAJ Moutet Jules J Niederegger Lukas L Simler Thomas T Nocton Grégory G Hess Corinna R CR

Inorganic chemistry 20201215 1

This work presents the synthesis and characterization of a 3d-4f bimetallic complex based on the redox-active macrocyclic biquinazoline ligand, Mabiq. The mixed Yb-Ni complex, [(Cp*)2Yb(Mabiq)Ni]BArF (3), was synthesized upon reaction of [NiII(Mabiq)]BArF (2) with (Cp*)2YbII(OEt2). The molecular structures of 3 and its sister complex, [(Cp*)2Yb(Mabiq)Ni][(Cp*)2Yb(OTf)2] (1), confir ...[more]

PMID: 33319984

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Project description:The reaction between the 2-(1-(2,6-di(pyrazol-1-yl)-4-methylpyridyl)-4,5-(4,5-bis(propylthio)-tetrathiafulvalenyl)-1H-benzimidazol-2-yl)-pyridine ligand (L), 1 equivalent of Ln(hfac)3·2H2O/Dy(tta)3·2H2O (hfac- = 1,1,1,5,5,5-hexafluoroacetylacetonate, tta- = 2-thenoyltrifluoroacetonate) and M(hfac)2·2H2O leads to the formation of heteroleptic 3d-4f dinuclear complexes of formula [MLn(hfac)5(L)]n (M(II) = Cd, Zn, Co, Mn, Ni and Ln(III) = Dy, Yb, Nd) and [ZnDy(tta)2(hfac)3(L)]·(CH2Cl2). Their X-ray structures reveal that the two coordination sites are occupied by one Ln(III) ion and one M(II) transition metal respectively. The M(II) ions are coordinated to the benzoimidazolylpyridine (bzip) moiety in a N2O4 coordination sphere, while the Ln(III) ions are coordinated to the 2,6-di(pyrazol-1-yl)-4-pyridine (dpp) moiety in a N3O6 surrounding. When Dy(III) ion is used a field-induced Single-Molecule Magnet (SMM) behavior is detected with a magnetic relaxation time slightly dependent to the nature of the vicinal divalent transition metal. On the other hand, when the Yb(III) is used, intense, moderated or quenched 2F5/2 → 2F7/2 NIR luminescence is observed when the Yb(III) ion is respectively associated with the Zn(II), Mn(II) and Ni(II)/Co(II) ion. The emission intensity can be modulated in function of the metal-to-ligand charge transfer and d-d transition intensities. The replacement of the divalent transition metal by a trivalent lanthanide leads to the formation of heteroleptic 4f-4f' dinuclear complexes of formula [Ln2-xLn'x(hfac)6(L)]·a(CH2Cl2)·b(C6H14) and [Dy1.11Nd0.89(tta)3(hfac)3(L)]. The coordination selectivity is based on the radius. Among the 4f-4f' series, the Dy(III) derivatives displayed such ion in N2O6 eight-coordinated sphere allowing the observation of SMM behavior. The three compounds [Dy1.21Nd0.79(hfac)6(L)]·2(CH2Cl2)·(C6H14), [Yb1.04Nd0.96(hfac)6(L)] and [YbPr(hfac)6(L)] displayed respectively Nd(III), modarated Yb(III) and intense Yb(III) NIR emissions.

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Influence of a Lanthanide Ion on the Ni Site of a Heterobimetallic 3d-4f Mabiq Complex.

Publications

Influence of a Lanthanide Ion on the Ni Site of a Heterobimetallic 3d-4f Mabiq Complex.

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