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Synthesis and Fluorescence Properties of Structurally Characterized Heterobimetalic Cu(II)?Na(I) Bis(salamo)-Based Complex Bearing Square Planar, Square Pyramid and Triangular Prism Geometries of Metal Centers.

ABSTRACT: A novel heterotrinuclear complex [Cu?(L)Na(µ-NO?)]?CH?OH?CHCl? derived from a symmetric bis(salamo)-type tetraoxime H?L having a naphthalenediol unit, was prepared and structurally characterized via means of elemental analyses, UV-Vis, FT-IR, fluorescent spectra and single-crystal X-ray diffraction. The heterobimetallic Cu(II)?Na(I) complex was acquired via the reaction of H?L with 2 equivalents of Cu(NO?)?·2H?O and 1 equivalent of NaOAc. Clearly, the heterotrinuclear Cu(II)?Na(I) complex has a 1:2:1 ligand-to-metal (Cu(II) and Na(I)) ratio. X-ray diffraction results exhibited the different geometric behaviors of the Na(I) and Cu(II) atoms in the heterotrinuclear complex; the both Cu(II) atoms are sited in the N?O? coordination environments of fully deprotonated (L)4? unit. One Cu(II) atom (Cu1) is five-coordinated and possesses a geometry of slightly distorted square pyramid, while another Cu(II) atom (Cu2) is four-coordination possessing a square planar coordination geometry. Moreover, the Na(I) atom is in the O? cavity and adopts seven-coordination with a geometry of slightly distorted single triangular prism. In addition, there are abundant supramolecular interactions in the Cu(II)?Na(I) complex. The fluorescence spectra showed the Cu(II)?Na(I) complex possesses a significant fluorescent quenching and exhibited a hypsochromic-shift compared with the ligand H?L.

SUBMITTER: Dong XY

PROVIDER: S-EPMC6102540 | biostudies-literature | 2018 Apr

REPOSITORIES: biostudies-literature

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Synthesis and Fluorescence Properties of Structurally Characterized Heterobimetalic Cu(II)⁻Na(I) Bis(salamo)-Based Complex Bearing Square Planar, Square Pyramid and Triangular Prism Geometries of Metal Centers.

Dong Xiu-Yan XY Zhao Qing Q Wei Zhi-Li ZL Mu Hao-Ran HR Zhang Han H Dong Wen-Kui WK

Molecules (Basel, Switzerland) 20180425 5

A novel heterotrinuclear complex [Cu₂(L)Na(<i>µ</i>-NO₃)]∙CH₃OH∙CHCl₃ derived from a symmetric bis(salamo)-type tetraoxime H₄L having a naphthalenediol unit, was prepared and structurally characterized via means of elemental analyses, UV-Vis, FT-IR, fluorescent spectra and single-crystal X-ray diffraction. The heterobimetallic Cu(II)⁻Na(I) complex was acquired via the reaction of H₄L with 2 equivalents of Cu(NO₃)₂·2H₂O and 1 equivalent of NaOAc. Clearly, the heterotrinuclear Cu(II)⁻Na(I) complex ...[more]

PMID: 29693609

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Project description:Among Earth-abundant catalyst systems, iron-carbene intermediates that perform C-C bond forming reactions such as cyclopropanation of olefins and C-H functionalization via carbene insertion are rare. Detailed descriptions of the possible electronic structures for iron-carbene bonds are imperative to obtain better mechanistic insights and enable rational catalyst design. Here, we report the first square-planar iron-carbene complex (MesPDPPh)Fe(CPh2), where [MesPDPPh]2- is the doubly deprotonated form of [2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine]. The compound was prepared via reaction of the disubstituted diazoalkane N2CPh2 with (MesPDPPh)Fe(thf) and represents a rare example of a structurally characterized, paramagnetic iron-carbene complex. Temperature-dependent magnetic susceptibility measurements and applied-field Mössbauer spectroscopic studies revealed an orbitally near-degenerate S = 1 ground state with large unquenched orbital angular momentum resulting in high magnetic anisotropy. Spin-Hamiltonian analysis indicated that this S = 1 spin system has uniaxial magnetic properties arising from a ground MS = ±1 non-Kramers doublet that is well-separated from the MS = 0 sublevel due to very large axial zero-field splitting (D = -195 cm-1, E/D = 0.02 estimated from magnetic susceptibility data). This remarkable electronic structure gives rise to a very large, positive magnetic hyperfine field of more than +60 T for the 57Fe nucleus along the easy magnetization axis observed by Mössbauer spectroscopy. Computational analysis with complete active space self-consistent field (CASSCF) calculations provides a detailed electronic structure analysis and confirms that (MesPDPPh)Fe(CPh2) exhibits a multiconfigurational ground state. The majority contribution originates from a configuration best described as a singlet carbene coordinated to an intermediate-spin FeII center with a (dxy)2{(dxz),(dz2)}3(dyz)1(dx2-y2)0 configuration featuring near-degenerate dxz and dz2 orbitals.

Dataset Information

Synthesis and Fluorescence Properties of Structurally Characterized Heterobimetalic Cu(II)?Na(I) Bis(salamo)-Based Complex Bearing Square Planar, Square Pyramid and Triangular Prism Geometries of Metal Centers.

Publications

Synthesis and Fluorescence Properties of Structurally Characterized Heterobimetalic Cu(II)⁻Na(I) Bis(salamo)-Based Complex Bearing Square Planar, Square Pyramid and Triangular Prism Geometries of Metal Centers.

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