Katsuhiro Aoyagi

Electron deficient porphyrins. 1. Tetrakis(trifluoromethyl)porphyrin and its metal complexes

Abstract 1,3,5,7-Tetrakis(trifluoromethyl)-2,4,6,8-tetraethylporphyrin and its metal (Cu(II), Zn(II), and Co(II) complexes have been prepared.

Magnetic properties of a penta-coordinated high-spin cobalt(II) complex: acetate-N-methyl-octaethylporphyrinato-cobalt(II)

It is shown by EPR and magnetic susceptibility (χ) measurements that acetate-N-methyl-octaethylporphyrinato-Co(II) has a high-spin ground state. The complex in toluene gives EPR spectra with g= 4.4 and 2.04 and χ with μeff= 4.4 BM and D ≈ 20 cm−1, which indicates square-pyramidal geometry around Co (II). Data for the undiluted system are analyzed in terms of a dimer model with a small exchange interaction.

Time-resolved resonance Raman spectra of octaethylporphinato copper(II) in the lowest excited triplet state

Abstract Time-resolved resonance Raman spectra were observed with the pump/probe technique using two 7 ns pulsed lasers for octaethylporphinato Cu(II) [(OEP)Cu] and its isotopomers (OEP-meso- d 4 and OEP- 15 N) in the lowest excited triplet state. Raman bands were assigned on the basis of depolarization ratios and isotope shifts. Then ν 2 , ν 3 and ν 4 modes of the macrocycle in the T 1 state were shifted to lower frequencies by 7, 37 and 57 cm −1 , respectively, compared with those of the ground state, but the peripheral ethyl internal modes were shifted little. The porphyrin skeletal modes exhibited significant broadening in the T 1 state but the ethyl modes did not.