Binuclear Rhodium(I) Complex of a Dimethylvinylene-Bridged Distorted Hexaphyrin(2.1.2.1.2.1)
Binuclear Rhodium(I) Complex of a Dimethylvinylene-Bridged Distorted Hexaphyrin(2.1.2.1.2.1)
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二甲基亚乙烯基桥扭曲六菲林的双核铑(I)络合物(2.1.2.1.2.1)
DOI：
10.1021/acs.inorgchem.1c02609
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发表时间：
2021
影响因子：
4.6
通讯作者：
Yamada Hiroko
中科院分区：
文献类型：
--
作者：
Xue Songlin;Liu Ningchao;Mei Peifeng;Kuzuhara Daiki;Aratani Naoki;Qiu Fengxian;Yamada Hiroko
以二吡咯单元间含有二甲基乙烯桥的六卟啉（2.1.2.1.2.1）为原料，合成了高度畸变的双核铑（I）配合物2 Rh。红外光谱、核磁共振氢谱和X-射线单晶衍射分析表明，配合物2 Rh由两个铑（I）离子与两个二吡咯基配位组成。Rh络合诱导了二甲基乙烯桥上的atrans-/cis-/trans-to-/cis-/cis-构象的转变。这是铑离子诱导卟啉衍生物顺反异构化的第一例。2 Rh的理论计算预测了分子内电荷转移吸收的存在，由于扭曲的分子结构。
A highly distorted binuclear rhodium(I) complex,2Rh, was successfully synthesized from hexaphyrin(2.1.2.1.2.1) containing dimethylvinylene-bridges between dipyrrin units. IR spectroscopy,1H NMR spectroscopy, and X-ray crystallography revealed that the complex2Rhconsists of two rhodium(I) ions coordinated to two dipyrrin units. Rh complexation induced a transformation from atrans-/cis-/trans-totrans-/cis-/cis-conformation on the dimethylvinylene-bridges. This is the first example of rhodium(I)-ion-inducedcis-/trans-isomerization in the porphyrin derivatives. Theoretical calculations of2Rhpredicted the presence of intramolecular charge-transfer absorption due to the distorted molecular structure.