Konarev D V, Neretin I S, Slovokhotov Y L, Yudanova E I, Drichko N V, Shul'ga Y M, Tarasov B P, Gumanov L L, Batsanov A S, Howard J A, Lyubovskaya R N
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Moscow Region.
Chemistry. 2001 Jun 18;7(12):2605-16. doi: 10.1002/1521-3765(20010618)7:12<2605::aid-chem26050>3.0.co;2-p.
New molecular complexes of fullerenes C60 and C70 with tetraphenylporphyrins [M(tpp)] in which M-H2, MnII, CoII, CuII, ZnII and Fe(III)Cl, have been synthesised. Crystal structures of two C60 complexes with H2TPP, which differ only in the number of benzene solvated molecules, and C60 and C70 complexes with [Cu(tpp)] have been studied. The fullerene molecules form a honeycomb motif in H2TPP.2C60. 3C6H6, puckered graphite-like layers in H2TPP.2C60.4C6H6, zigzag chains in [Cu(tpp)].C70.1.5C7H8.0.5C2HCl3 and columns in [Cu(tpp)]2.C60. H2TPP has van der Waals contacts with C60 through nitrogen atoms and phenyl groups. Copper atoms of the [Cu(tpp)] molecules are weakly coordinated with C70, but form no shortened contacts with C60. The formation of molecular complexes with fullerenes affects the ESR spectra of [M(tpp)] (M = Mn, Co and Cu). [Mn(tpp)] in the complex with C70 lowers its spin state from S = 5/2 to S = 1/2, whereas [Co(tpp)] and [Cu(tpp)] change the constants of hyperfine interaction. ESR, IR, UV-visible and X-ray photoelectron spectroscopic data show no noticeable charge transfer from the porphyrinate to the fullerene molecules.
已合成了富勒烯C60和C70与四苯基卟啉[M(tpp)]（其中M为H2、MnII、CoII、CuII、ZnII和Fe(III)Cl）的新型分子复合物。研究了两种仅在苯溶剂化分子数量上有所不同的C60与H2TPP的复合物以及C60和C70与[Cu(tpp)]的复合物的晶体结构。在H2TPP·2C60·3C6H6中，富勒烯分子形成蜂窝状图案；在H2TPP·2C60·4C6H6中，形成褶皱的类石墨层；在[Cu(tpp)]·C70·1.5C7H8·0.5C2HCl3中，形成锯齿链；在[Cu(tpp)]2·C60中，形成柱状结构。H2TPP通过氮原子和苯基与C60存在范德华接触。[Cu(tpp)]分子中的铜原子与C70弱配位，但与C60没有形成缩短的接触。与富勒烯形成分子复合物会影响[M(tpp)]（M = Mn、Co和Cu）的电子顺磁共振（ESR）光谱。与C70形成复合物的[Mn(tpp)]将其自旋态从S = 5/2降低到S = 1/2，而[Co(tpp)]和[Cu(tpp)]则改变了超精细相互作用常数。电子顺磁共振、红外、紫外可见和X射线光电子能谱数据表明，没有明显的电荷从卟啉酸盐转移到富勒烯分子上。
