期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 13, 期 5, 页码 1620-1628出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200601304
关键词
conjugation heterometallic complexes; HOMOLUMO gap; macrocyclic ligands; porphyrinoids
meso-Pentafluorophenyl-substituted [40]nonaphyrin-(1.1.1.1.1.1.1.1.1) 3 has been prepared by using a stepwise ring-size-selective synthesis, and has been reduced with NaBH, to [42]nonaphyin(1.1.1.1.1.1.1.1.1.1) 5. Structurally, 3 is characterized by a figure-of-eight shape, consisting of a porphyrin-like tetrapyrrolic segment and a hexaphyrin-like hexapyrrolic segment, whereas 5 has been found to adopt a distorted nonplanar butterfly-like shape. In the mono-metal complexes 6 and 7, a Zn-II or Cu-II ion is bound by the porphyrin-like tetrapyrrolic segment, maintaining the overall structure of 3. Similarly to 3, complexes 6 and 7 are interconvertible with the corresponding complexes 9 and 10 through two-electron reduction with NaBH, and oxidation with DDQ. The metal-free hexaphyrin-like segments of 6 and 7 have been shown to serve as a suitable platform for the complexation of two palladium ions, providing hetero-trinuclear metal complexes 11 (Zn-II-Pd-II-Pd-II) and 13 (Cu-II-Pd-II-Pd-II) in high yields, in which the Zn or Cu ion resides at the same porphyrin-like segment, and one Pd ion is bound in an NNCC fashion through double C-H bond activation while the other is bound in an NNC fashion with single C-H bond activation. Multimetal complexes 11, 12, and 13 exhibit small electrochemical HOMO-LUMO gaps (< 0.6 eV), despite their nonplanar conformations.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据