四个新的混合3(4),12(13),21(22),30(31)-四(叔丁基)酞菁到四(4-吡啶基)卟啉到稀土三层复合物M 2(TPyP)(TBPc )2(M˭Ce,Sm,Tb和Tm)通过在回流的1,2,4-溶液中用相应的均取代的双(邻苯二甲腈基)稀土配合物M(TBPc)2处理M(acac)(TPyP)制备三氯苯(TCB),分别分别用于轻,中和重稀土。取代的酞菁双阴离子Pc(TBPc)2-的典型IR标记带在ca处显示强带。1323 cm -1,归因于吡咯C˭C拉伸。大约TPyP 2- IR标记带。这些化合物未观察到1270–1300 cm -1。吡咯C˭C和氮杂C˭N延伸以及异吲哚延伸均在1500 cm - 1处形成的非常强的谱带是(TBPc)2−的标记拉曼谱带。通过循环伏安法和差分脉冲伏安法研究了它们的电化学性能。四种配合物的特征还在于EA,MS和UV-vis光谱。
Cationic lanthanide monoporphyrinates with Sm, Eu, Gd and Tb, synthesis and spectroscopic properties in aqueous and non-aqueous media
作者:G.A. Spyroulias、M.P. Sioubara、A.G. Coutsolelos
DOI:10.1016/0277-5387(95)00175-r
日期:1995.12
The synthesis of a new series of cationic monoporphyrinates with ''light'' lanthanide ions is reported. The meso-tetrakis(4-pyridyl)porphyrin, (tpyp)H-2, was used as the tetrapyrrole ligand, and the metallation reaction with the lanthanide ions in acetyl-acetonato form, leading to Ln(tpyp)acac, where Ln = Sm, Eu, Gd and Tb, was carried out. The cationic monoporphyrinates, Ln(tmepyp)acac, were synthesized via the corresponding Ln(tpyp)acac. These complexes are freely soluble in aqueous and non-aqueous solutions, like MeOH, H2O or N,N-dimethylformamide. Their spectroscopic properties in water and DMF solutions are reported. All the complexes were characterized on the basis of their UV-vis, IR and ESR data. No ESR spectra were obtained for cationic porphyrins in DMF for Sm, Eu and Tb, while the spectra of Gd(tmepyp)acac in DMF exhibits smaller Delta H-pp (103.1 G) among the spectra of Gd-III complexes. The unexpected broad signal of Eu(t-mepyp)acac, Delta H-pp = 126.9 G, in H2O is discussed in terms of the formal oxidation state +2 for the central ion.