Dataset Information

Cyclic [Cu-biRadical]₂ Secondary Building Unit in 2p-3d and 2p-3d-4f Complexes: Crystal Structure and Magnetic Properties.

ABSTRACT: Employing the new nitronyl nitroxide biradical ligand biNIT-3Py-5-Ph (2-(5-phenyl-3-pyridyl)-bis(4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide)), a 16-spin Cu-radical complex, [Cu₈(biNIT-3Py-5-Ph)₄(hfac)₁₆] 1, and three 2p-3d-4f chain complexes, {[Ln(hfac)₃][Cu(hfac)₂]₂(biNIT-3Py-5-Ph)₂}_n (Ln^Ⅲ= Gd 2, Tb 3, Dy 4; hfac = hexafluoroacetylacetonate), have been prepared and characterized. X-ray crystallographic analysis revealed in all derivatives a common cyclic [Cu-biNIT]₂ secondary building unit in which two bi-NIT-3Py-5-Ph biradical ligands and two Cu^II ions are associated via the pyridine N atoms and NO units. For complex 1, two such units assemble with four additional Cu^II ions to form a discrete complex involving 16 S = 1/2 spin centers. For complexes 2-4, the [Cu-biNIT]₂ units are linked by Ln^III ions via NO groups in a 1D coordination polymer. Magnetic studies show that the coordination of the aminoxyl groups with Cu or Ln ions results in behaviors combining ferromagnetic and antiferromagnetic interactions. No slow magnetic relaxation behavior was observed for Tb and Dy derivatives.

SUBMITTER: Wang XT

PROVIDER: S-EPMC10058193 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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Publications

Cyclic [Cu-biRadical]2 Secondary Building Unit in 2p-3d and 2p-3d-4f Complexes: Crystal Structure and Magnetic Properties.

Wang Xiao-Tong XT Huang Xiao-Hui XH Song Hong-Wei HW Ma Yue Y Li Li-Cun LC Sutter Jean-Pascal JP

Molecules (Basel, Switzerland) 20230309 6

Employing the new nitronyl nitroxide biradical ligand biNIT-3Py-5-Ph (2-(5-phenyl-3-pyridyl)-bis(4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide)), a 16-spin Cu-radical complex, [Cu8(biNIT-3Py-5-Ph)4(hfac)16] 1, and three 2p-3d-4f chain complexes, {[Ln(hfac)3][Cu(hfac)2]2(biNIT-3Py-5-Ph)2}n (LnⅢ= Gd 2, Tb 3, Dy 4; hfac = hexafluoroacetylacetonate), have been prepared and c ...[more]

PMID: 36985497

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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.

Dataset Information

Cyclic [Cu-biRadical]₂ Secondary Building Unit in 2p-3d and 2p-3d-4f Complexes: Crystal Structure and Magnetic Properties.

Publications

Cyclic [Cu-biRadical]<sub>2</sub> Secondary Building Unit in 2p-3d and 2p-3d-4f Complexes: Crystal Structure and Magnetic Properties.

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