Heterodinuclear Complexes Containing d- and f-block Elements

Synthesis, Structural Characterization, and Metal-Metal Interactions of Novel Chromium(III)-Lanthanide(III) Compounds Bridged by Oxalate

Takayuki Sanada, Takayoshi Suzuki, Takafumi Yoshida, Sumio Kaizaki

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Abstract

The reaction of Ln(III) ions with a tripodal ligand HBpz3- (hydrotris(pyrazol-1-yl)borate) and a "complex ligand" [Cr(acac)2(ox)]- (acac- = acetylacetonate, ox2- = oxalate) in aqueous solution afforded a series of the novel 3d-4f heterodinuclear complexes [(acac)2Cr(ox)Ln(HBpz3)2] (Ln = Eu (1), Gd (2), Tb (3), Yb (4), Lu (5)). The crystal structure of 4 has been determined by X-ray diffraction. Complex 4 crystallizes in monoclinic space group P2/n, of which the cell parameters are a = 8.594(3) Å, b = 18.538(4) Å, c = 12.093(2) Å, β = 93.71(2)°, and Z = 2. The Yb atom has an eight-coordinate distorted square antiprismatic coordination geometry. The intramolecular Cr⋯Yb distance is 5.631(1) Å. The magnetic susceptibility data for complex 2 showed that the CrIII-GdIII interaction is weakly antiferromagnetic with an exchange coupling constant JCrGd = -0.09 cm-1. The luminescence measurements demonstrated the energy transfers for both Ln(III) → Cr(III) and Cr(III) → Ln(III), of which the degree of emission quenching depends on the energy gap of the excited levels in two metal centers. These results reveal that the metal-metal interactions between Cr(III) and Ln(III) are very weak in magnetic interaction but are strong from the viewpoint of energy transfer.

Original languageEnglish
Pages (from-to)4712-4717
Number of pages6
JournalInorganic Chemistry
Volume37
Issue number18
Publication statusPublished - Sep 7 1998
Externally publishedYes

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Bridged-Ring Compounds
Lanthanoid Series Elements
Oxalates
Chromium
oxalates
chromium
Metals
Ligands
ligands
synthesis
metals
Energy transfer
energy transfer
interactions
Exchange coupling
Borates
borates
Magnetic susceptibility
Luminescence
Quenching

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{bcd855d60030420a8bfcf7eb7645addf,
title = "Heterodinuclear Complexes Containing d- and f-block Elements: Synthesis, Structural Characterization, and Metal-Metal Interactions of Novel Chromium(III)-Lanthanide(III) Compounds Bridged by Oxalate",
abstract = "The reaction of Ln(III) ions with a tripodal ligand HBpz3- (hydrotris(pyrazol-1-yl)borate) and a {"}complex ligand{"} [Cr(acac)2(ox)]- (acac- = acetylacetonate, ox2- = oxalate) in aqueous solution afforded a series of the novel 3d-4f heterodinuclear complexes [(acac)2Cr(ox)Ln(HBpz3)2] (Ln = Eu (1), Gd (2), Tb (3), Yb (4), Lu (5)). The crystal structure of 4 has been determined by X-ray diffraction. Complex 4 crystallizes in monoclinic space group P2/n, of which the cell parameters are a = 8.594(3) {\AA}, b = 18.538(4) {\AA}, c = 12.093(2) {\AA}, β = 93.71(2)°, and Z = 2. The Yb atom has an eight-coordinate distorted square antiprismatic coordination geometry. The intramolecular Cr⋯Yb distance is 5.631(1) {\AA}. The magnetic susceptibility data for complex 2 showed that the CrIII-GdIII interaction is weakly antiferromagnetic with an exchange coupling constant JCrGd = -0.09 cm-1. The luminescence measurements demonstrated the energy transfers for both Ln(III) → Cr(III) and Cr(III) → Ln(III), of which the degree of emission quenching depends on the energy gap of the excited levels in two metal centers. These results reveal that the metal-metal interactions between Cr(III) and Ln(III) are very weak in magnetic interaction but are strong from the viewpoint of energy transfer.",
author = "Takayuki Sanada and Takayoshi Suzuki and Takafumi Yoshida and Sumio Kaizaki",
year = "1998",
month = "9",
day = "7",
language = "English",
volume = "37",
pages = "4712--4717",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "18",

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TY - JOUR

T1 - Heterodinuclear Complexes Containing d- and f-block Elements

T2 - Synthesis, Structural Characterization, and Metal-Metal Interactions of Novel Chromium(III)-Lanthanide(III) Compounds Bridged by Oxalate

AU - Sanada, Takayuki

AU - Suzuki, Takayoshi

AU - Yoshida, Takafumi

AU - Kaizaki, Sumio

PY - 1998/9/7

Y1 - 1998/9/7

N2 - The reaction of Ln(III) ions with a tripodal ligand HBpz3- (hydrotris(pyrazol-1-yl)borate) and a "complex ligand" [Cr(acac)2(ox)]- (acac- = acetylacetonate, ox2- = oxalate) in aqueous solution afforded a series of the novel 3d-4f heterodinuclear complexes [(acac)2Cr(ox)Ln(HBpz3)2] (Ln = Eu (1), Gd (2), Tb (3), Yb (4), Lu (5)). The crystal structure of 4 has been determined by X-ray diffraction. Complex 4 crystallizes in monoclinic space group P2/n, of which the cell parameters are a = 8.594(3) Å, b = 18.538(4) Å, c = 12.093(2) Å, β = 93.71(2)°, and Z = 2. The Yb atom has an eight-coordinate distorted square antiprismatic coordination geometry. The intramolecular Cr⋯Yb distance is 5.631(1) Å. The magnetic susceptibility data for complex 2 showed that the CrIII-GdIII interaction is weakly antiferromagnetic with an exchange coupling constant JCrGd = -0.09 cm-1. The luminescence measurements demonstrated the energy transfers for both Ln(III) → Cr(III) and Cr(III) → Ln(III), of which the degree of emission quenching depends on the energy gap of the excited levels in two metal centers. These results reveal that the metal-metal interactions between Cr(III) and Ln(III) are very weak in magnetic interaction but are strong from the viewpoint of energy transfer.

AB - The reaction of Ln(III) ions with a tripodal ligand HBpz3- (hydrotris(pyrazol-1-yl)borate) and a "complex ligand" [Cr(acac)2(ox)]- (acac- = acetylacetonate, ox2- = oxalate) in aqueous solution afforded a series of the novel 3d-4f heterodinuclear complexes [(acac)2Cr(ox)Ln(HBpz3)2] (Ln = Eu (1), Gd (2), Tb (3), Yb (4), Lu (5)). The crystal structure of 4 has been determined by X-ray diffraction. Complex 4 crystallizes in monoclinic space group P2/n, of which the cell parameters are a = 8.594(3) Å, b = 18.538(4) Å, c = 12.093(2) Å, β = 93.71(2)°, and Z = 2. The Yb atom has an eight-coordinate distorted square antiprismatic coordination geometry. The intramolecular Cr⋯Yb distance is 5.631(1) Å. The magnetic susceptibility data for complex 2 showed that the CrIII-GdIII interaction is weakly antiferromagnetic with an exchange coupling constant JCrGd = -0.09 cm-1. The luminescence measurements demonstrated the energy transfers for both Ln(III) → Cr(III) and Cr(III) → Ln(III), of which the degree of emission quenching depends on the energy gap of the excited levels in two metal centers. These results reveal that the metal-metal interactions between Cr(III) and Ln(III) are very weak in magnetic interaction but are strong from the viewpoint of energy transfer.

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