TY - JOUR
T1 - Heterodinuclear MIICuII complexes of a constrained macrocyclic compartmental ligand. EPR studies of spin-coupled MnIICuII (ST=2) and NiIICuII (ST=1/2)
AU - Hori, Akiko
AU - Mitsuka, Yuko
AU - Ohba, Masaaki
AU - Kawa, Hisashi
N1 - Funding Information:
This work was supported by a grant-in-aid for scientific research on the priority area ‘Metal-assembled Complexes’ (no. 10149106), a grant-in-aid for COE research ‘Design and Control of Advanced Molecular Assembly System’ (no. 08CE2005) and a grant-in-aid for scientific research program (no. 13640561) from the Ministry of Education and Science, Japan. One of the authors (M.O.) thanks Precursory Research for Embryonic Science and Technology (PRESTO), JST for financial support. We thank Professor Yoshihisa Matsuda of Kyushu University for valuable suggestions in EPR analyses.
PY - 2002/9/26
Y1 - 2002/9/26
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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U2 - 10.1016/S0020-1693(02)01099-X
DO - 10.1016/S0020-1693(02)01099-X
M3 - Article
AN - SCOPUS:0037179947
SN - 0020-1693
VL - 337
SP - 113
EP - 121
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -