Tamiaki Hitoshi, Amakawa Masaaki, Holzwarth Alfred R, Schaffner Kurt
Department of Bioscience and Biotechnology, Faculty of Science and Engineering, Ritsumeikan University, Kusatsu, Shiga, 525-8577, Japan,
Photosynth Res. 2002;71(1-2):59-67. doi: 10.1023/A:1014951513848.
Metal 3(1)-hydroxy-13(1)-oxo-chlorins were systematically prepared and their visible and circular dichroism spectra were measured in a solution. All the synthetic complexes were monomeric in tetrahydrofuran. The Ni/Cu/Pd/Ag(II) complexes were still monomeric after dilution with 99-fold hexane. In contrast, the Co(II) complex, as well as the Mg/Zn/Cd(II) complexes, self-aggregated in 1% (v/v) tetrahydrofuran-hexane to form oligomers. In the less polar organic solvent, the Mn(III) complex fully dimerized and the Fe(III) complex partially dimerized. Infrared spectra of the synthetic metal chlorins in solid thin films revealed that the Ni/Cu/Pd/Ag(II) and ClFe(III) chlorins were 4- and 5-coordinated monomers, respectively, the AcOMn(III) chlorin formed a 6-coordinated dimer by mutual coordination of 3(1)-OetaetaetaMn, and the Co(II) chlorin as well as the Mg/Zn/Cd(II) chlorins self-aggregated by 13-C=OetaetaetaO-Hetaetaetametal to form large oligomers.
系统地制备了金属3(1)-羟基-13(1)-氧代二氢卟吩，并在溶液中测量了它们的可见光谱和圆二色光谱。所有合成配合物在四氢呋喃中均为单体。用99倍己烷稀释后，Ni/Cu/Pd/Ag(II)配合物仍为单体。相比之下，Co(II)配合物以及Mg/Zn/Cd(II)配合物在1%（v/v）四氢呋喃-己烷中自聚集形成低聚物。在极性较小的有机溶剂中，Mn(III)配合物完全二聚，Fe(III)配合物部分二聚。固体薄膜中合成金属二氢卟吩的红外光谱表明，Ni/Cu/Pd/Ag(II)和ClFe(III)二氢卟吩分别为4配位和5配位单体，AcOMn(III)二氢卟吩通过3(1)-OηηηMn的相互配位形成6配位二聚体，Co(II)二氢卟吩以及Mg/Zn/Cd(II)二氢卟吩通过13-C=OηηηO-Hηηη金属自聚集形成大的低聚物。
