Homodinuclear lanthanoid(III) dithiocarbamato complexes bridged by 2,2′-bipyrimidine: Syntheses, structures and spectroscopic properties

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Abstract

Four new homodinuclear lanthanoid(III) dithiocarbamato (RR′dtc) complexes bridged by 2,2′-bipyrimidine (bpm) of the form [{Ln(RR′dtc)3}2(µ-bpm)] {Ln = Nd or Eu; RR′ = dimethyl- (Me2) or pyrrolidine- (pyr)} were prepared and their crystal structures and spectroscopic properties were characterized. The crystallographic studies revealed that all of the complexes possess a similar structural motif with an 8:8-coordination geometry, in which the bpm ligand bridges two LnIII centers in the κ2N1,1′2N3,3′ mode and three RR′dtc ligands coordinate to each LnIII center. The complexes exhibit weak but relatively sharp f–f transition bands in the absorption and magnetic circular dichroism (MCD) spectra recorded in the visible region. The MCD spectral studies demonstrated the magneto-optical behavior of the complexes. The spectral features of the dithiocarbamato complexes were distinctly different from those of their β-diketonato analogues, suggesting the coordination environment around the LnIII center influences the electronic structure and spectroscopic symmetry of the complexes in solution.

Original languageEnglish
Pages (from-to)515-522
Number of pages8
JournalPolyhedron
Volume171
DOIs
Publication statusPublished - Oct 1 2019

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Lanthanoid Series Elements
Dichroism
Ligands
dichroism
synthesis
Electronic structure
ligands
Crystal structure
Geometry
analogs
electronic structure
crystal structure
symmetry
geometry
pyrrolidine

Keywords

  • 2,2′-Bipyrimidine
  • Dithiocarbamate
  • Electronic structure
  • Homodinuclear
  • Magnetic circular dichroism

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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title = "Homodinuclear lanthanoid(III) dithiocarbamato complexes bridged by 2,2′-bipyrimidine: Syntheses, structures and spectroscopic properties",
abstract = "Four new homodinuclear lanthanoid(III) dithiocarbamato (RR′dtc−) complexes bridged by 2,2′-bipyrimidine (bpm) of the form [{Ln(RR′dtc)3}2(µ-bpm)] {Ln = Nd or Eu; RR′ = dimethyl- (Me2) or pyrrolidine- (pyr)} were prepared and their crystal structures and spectroscopic properties were characterized. The crystallographic studies revealed that all of the complexes possess a similar structural motif with an 8:8-coordination geometry, in which the bpm ligand bridges two LnIII centers in the κ2N1,1′:κ2N3,3′ mode and three RR′dtc− ligands coordinate to each LnIII center. The complexes exhibit weak but relatively sharp f–f transition bands in the absorption and magnetic circular dichroism (MCD) spectra recorded in the visible region. The MCD spectral studies demonstrated the magneto-optical behavior of the complexes. The spectral features of the dithiocarbamato complexes were distinctly different from those of their β-diketonato analogues, suggesting the coordination environment around the LnIII center influences the electronic structure and spectroscopic symmetry of the complexes in solution.",
keywords = "2,2′-Bipyrimidine, Dithiocarbamate, Electronic structure, Homodinuclear, Magnetic circular dichroism",
author = "Abdallah Yakubu and Takayoshi Suzuki and Masakazu Kita",
year = "2019",
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language = "English",
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journal = "Polyhedron",
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T1 - Homodinuclear lanthanoid(III) dithiocarbamato complexes bridged by 2,2′-bipyrimidine

T2 - Syntheses, structures and spectroscopic properties

AU - Yakubu, Abdallah

AU - Suzuki, Takayoshi

AU - Kita, Masakazu

PY - 2019/10/1

Y1 - 2019/10/1

N2 - Four new homodinuclear lanthanoid(III) dithiocarbamato (RR′dtc−) complexes bridged by 2,2′-bipyrimidine (bpm) of the form [{Ln(RR′dtc)3}2(µ-bpm)] {Ln = Nd or Eu; RR′ = dimethyl- (Me2) or pyrrolidine- (pyr)} were prepared and their crystal structures and spectroscopic properties were characterized. The crystallographic studies revealed that all of the complexes possess a similar structural motif with an 8:8-coordination geometry, in which the bpm ligand bridges two LnIII centers in the κ2N1,1′:κ2N3,3′ mode and three RR′dtc− ligands coordinate to each LnIII center. The complexes exhibit weak but relatively sharp f–f transition bands in the absorption and magnetic circular dichroism (MCD) spectra recorded in the visible region. The MCD spectral studies demonstrated the magneto-optical behavior of the complexes. The spectral features of the dithiocarbamato complexes were distinctly different from those of their β-diketonato analogues, suggesting the coordination environment around the LnIII center influences the electronic structure and spectroscopic symmetry of the complexes in solution.

AB - Four new homodinuclear lanthanoid(III) dithiocarbamato (RR′dtc−) complexes bridged by 2,2′-bipyrimidine (bpm) of the form [{Ln(RR′dtc)3}2(µ-bpm)] {Ln = Nd or Eu; RR′ = dimethyl- (Me2) or pyrrolidine- (pyr)} were prepared and their crystal structures and spectroscopic properties were characterized. The crystallographic studies revealed that all of the complexes possess a similar structural motif with an 8:8-coordination geometry, in which the bpm ligand bridges two LnIII centers in the κ2N1,1′:κ2N3,3′ mode and three RR′dtc− ligands coordinate to each LnIII center. The complexes exhibit weak but relatively sharp f–f transition bands in the absorption and magnetic circular dichroism (MCD) spectra recorded in the visible region. The MCD spectral studies demonstrated the magneto-optical behavior of the complexes. The spectral features of the dithiocarbamato complexes were distinctly different from those of their β-diketonato analogues, suggesting the coordination environment around the LnIII center influences the electronic structure and spectroscopic symmetry of the complexes in solution.

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