Heterodinuclear MIICuII complexes of a constrained macrocyclic compartmental ligand. EPR studies of spin-coupled MnIICuII (ST=2) and NiIICuII (ST=1/2)

Akiko Hori, Yuko Mitsuka, Masaaki Ohba, Hisashi Kawa

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

A phenol-based macrocyclic compartmental ligand (L)2-, having an N(amine)2O2 metal-binding site with 1,3-trimethylene chain between the two aminic nitrogen atoms and an N(imine)2O2 site with 1,8-naphthalene chain between the two iminic nitrogen atoms, has afforded the following heterodinuclear MIICuII complexes, [MCu(L)(dmf)2](ClO4)2 (M=Mn (1), Co (2), Ni (3), Zn (4)). X-ray crystallographic studies for 1-4 demonstrate that the MII resides in the N(amine)2O2 site and the CuII in the N(imine)2O2 site of the constrained macrocyclic ligand. The MII has a six-coordinate geometry together with two dmf molecules at the axial site and the CuII has a square-pyramidal geometry with a perchlorate oxygen atom at the apical site. Magnetic, visible spectral and electrochemical properties of the complexes are examined. A frozen dmf solution of 1 at liquid nitrogen temperature shows an EPR signal with a Mn hyperfine structure (AMn=103×10-4 cm-1) at ∼2400 Ga, which is attributed to the ST=2 ground state of the spin-coupled MnII (S=5/2)-CuII (S=1/2). A qualitative analysis is made for the EPR of 1 in comparison with the EPR of the ST=1/2 state of spin-coupled NiII (S=1)-CuII (S=1/2) of 3.

Original languageEnglish
Pages (from-to)113-121
Number of pages9
JournalInorganica Chimica Acta
Volume337
DOIs
Publication statusPublished - 2002 Sep 26
Externally publishedYes

Fingerprint

nitrogen atoms
imines
Paramagnetic resonance
amines
Imines
Ligands
Atoms
ligands
Amines
qualitative analysis
Nitrogen
perchlorates
geometry
hyperfine structure
naphthalene
liquid nitrogen
phenols
oxygen atoms
Geometry
Liquid nitrogen

Keywords

  • Dinuclear complexes
  • EPR spectra
  • Macrocyclic ligands
  • Magnetic interaction
  • X-ray crystal structures

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Heterodinuclear MIICuII complexes of a constrained macrocyclic compartmental ligand. EPR studies of spin-coupled MnIICuII (ST=2) and NiIICuII (ST=1/2). / Hori, Akiko; Mitsuka, Yuko; Ohba, Masaaki; Kawa, Hisashi.

In: Inorganica Chimica Acta, Vol. 337, 26.09.2002, p. 113-121.

Research output: Contribution to journalArticle

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abstract = "A phenol-based macrocyclic compartmental ligand (L)2-, having an N(amine)2O2 metal-binding site with 1,3-trimethylene chain between the two aminic nitrogen atoms and an N(imine)2O2 site with 1,8-naphthalene chain between the two iminic nitrogen atoms, has afforded the following heterodinuclear MIICuII complexes, [MCu(L)(dmf)2](ClO4)2 (M=Mn (1), Co (2), Ni (3), Zn (4)). X-ray crystallographic studies for 1-4 demonstrate that the MII resides in the N(amine)2O2 site and the CuII in the N(imine)2O2 site of the constrained macrocyclic ligand. The MII has a six-coordinate geometry together with two dmf molecules at the axial site and the CuII has a square-pyramidal geometry with a perchlorate oxygen atom at the apical site. Magnetic, visible spectral and electrochemical properties of the complexes are examined. A frozen dmf solution of 1 at liquid nitrogen temperature shows an EPR signal with a Mn hyperfine structure (AMn=103×10-4 cm-1) at ∼2400 Ga, which is attributed to the ST=2 ground state of the spin-coupled MnII (S=5/2)-CuII (S=1/2). A qualitative analysis is made for the EPR of 1 in comparison with the EPR of the ST=1/2 state of spin-coupled NiII (S=1)-CuII (S=1/2) of 3.",
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T1 - Heterodinuclear MIICuII complexes of a constrained macrocyclic compartmental ligand. EPR studies of spin-coupled MnIICuII (ST=2) and NiIICuII (ST=1/2)

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AU - Kawa, Hisashi

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N2 - A phenol-based macrocyclic compartmental ligand (L)2-, having an N(amine)2O2 metal-binding site with 1,3-trimethylene chain between the two aminic nitrogen atoms and an N(imine)2O2 site with 1,8-naphthalene chain between the two iminic nitrogen atoms, has afforded the following heterodinuclear MIICuII complexes, [MCu(L)(dmf)2](ClO4)2 (M=Mn (1), Co (2), Ni (3), Zn (4)). X-ray crystallographic studies for 1-4 demonstrate that the MII resides in the N(amine)2O2 site and the CuII in the N(imine)2O2 site of the constrained macrocyclic ligand. The MII has a six-coordinate geometry together with two dmf molecules at the axial site and the CuII has a square-pyramidal geometry with a perchlorate oxygen atom at the apical site. Magnetic, visible spectral and electrochemical properties of the complexes are examined. A frozen dmf solution of 1 at liquid nitrogen temperature shows an EPR signal with a Mn hyperfine structure (AMn=103×10-4 cm-1) at ∼2400 Ga, which is attributed to the ST=2 ground state of the spin-coupled MnII (S=5/2)-CuII (S=1/2). A qualitative analysis is made for the EPR of 1 in comparison with the EPR of the ST=1/2 state of spin-coupled NiII (S=1)-CuII (S=1/2) of 3.

AB - A phenol-based macrocyclic compartmental ligand (L)2-, having an N(amine)2O2 metal-binding site with 1,3-trimethylene chain between the two aminic nitrogen atoms and an N(imine)2O2 site with 1,8-naphthalene chain between the two iminic nitrogen atoms, has afforded the following heterodinuclear MIICuII complexes, [MCu(L)(dmf)2](ClO4)2 (M=Mn (1), Co (2), Ni (3), Zn (4)). X-ray crystallographic studies for 1-4 demonstrate that the MII resides in the N(amine)2O2 site and the CuII in the N(imine)2O2 site of the constrained macrocyclic ligand. The MII has a six-coordinate geometry together with two dmf molecules at the axial site and the CuII has a square-pyramidal geometry with a perchlorate oxygen atom at the apical site. Magnetic, visible spectral and electrochemical properties of the complexes are examined. A frozen dmf solution of 1 at liquid nitrogen temperature shows an EPR signal with a Mn hyperfine structure (AMn=103×10-4 cm-1) at ∼2400 Ga, which is attributed to the ST=2 ground state of the spin-coupled MnII (S=5/2)-CuII (S=1/2). A qualitative analysis is made for the EPR of 1 in comparison with the EPR of the ST=1/2 state of spin-coupled NiII (S=1)-CuII (S=1/2) of 3.

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