| Summary: | 碩士 === 國立中興大學 === 化學系所 === 102 === We use isopropyl benzyl bromide as alkylation reagent to react with N-confused porphyrin (NCP) to afford 2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21-carbaporphyrin [2-NCH2-p-C6H4-isoC3H7NCTPPH; 2]. Then we use Ni(OAc)2∙4H2O, PdCl2, PtCl2 and CoCl2∙6H2O as metal source to react with (2) seperately to get four NCP metal complexes: (2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′,N′′) nickel(II) [Ni(2-NCH2-p-C6H4-isoC3H7NCTPP); 3], (2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′,N′′) palladium(II) [Pd(2-NCH2-p-C6H4-isoC3H7NCTPP); 4], (2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′,N′′) platinum(II) [Pt(2-NCH2-p-C6H4-isoC3H7NCTPP); 5], and chloro(2-aza-2-[p-(isopropyl)benzyl]-5,10,15,20-tetraphenyl-21- p-xylyl-21-carbaporphyrinato-N,N′,N′′) cobalt(II) [Co(2-NCH2-p-C6H4-isoC3H7-21-CH2-p-C6H4CH3-NCTPP)Cl; 6].
Appling X-ray single-crystal diffractometer, Nuclear magnetic resonance spectrometer, Electron paramagnetic resonance spectrometer, Superconducting quantum interference device magnetometer, UV-visible spectrophotometer, UV-visible-NIR spectrophotometer, Elemental analyzer, Mass spectrometer to characterize and study the crystal structures of NCP metal complexes and their physical chemistry property.
The crystal structures of free base (2), diamagnetic complexes (3), (4), (5) and paramagnetic complex (6) were determined. The coordination sphere around Ni2+, Pd2+ and Pt2+ ions in 3 - 5 are distorted square planar (DSP), whereas for Co2+ in 6, it is distorted tetrahedron (DT). The effective g value, geff = [gx(eff), gy(eff), gz(eff)] = [1.92, 3.73, 6.18] measured from the perpendicular polarization of X-band EPR spectra for 6 in toluene at 4 K is consistent with a 4A2(F) ground term for a high spin mononuclear cobalt (II) (S = 3/2) in 6. The magnitudes of axial (D) and rhombic (E) zero-field splitting (ZFS) for the mononuclear Co(II) in 6 were determined approximately as 29.35 cm-1 and 6.46 cm-1.
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