Longevial Jean-François, Lo Mamadou, Lebrun Aurélien, Laurencin Danielle, Clément Sébastien, Richeter Sébastien
ICGM, Univ Montpellier, CNRS, ENSCM, CC 1701, Campus Triolet, Place Eugène Bataillon, Montpellier, France.
Dalton Trans. 2020 Jun 7;49(21):7005-7014. doi: 10.1039/d0dt00594k. Epub 2020 Mar 18.
Janus bis(N-heterocyclic carbenes) composed of a porphyrin core with two N-heterocyclic carbene (NHC) heads fused to opposite pyrroles were used as bridging ligands for the preparation of metal complexes. We first focused our attention on the synthesis of gold(i) chloride complexes [(NHC)AuCl] and investigated the substitution of the chloride ligand by acetylides to obtain the corresponding [(NHC)AuC[triple bond, length as m-dash]CR] complexes. Polyacetylides were then used to obtain molecular multiporphyrinic systems with porphyrins fused to only one NHC ligand, while main-chain organometallic polymers (MCOPs) were obtained when using Janus porphyrin bis(NHCs). Interestingly, MCOPs incorporating zinc(ii) porphyrins proved to be efficient as heterogeneous photocatalysts for the generation of singlet oxygen upon visible light irradiation.
由卟啉核心和两个与相对吡咯稠合的N-杂环卡宾（NHC）端基组成的双（N-杂环卡宾）型Janus分子被用作制备金属配合物的桥连配体。我们首先将注意力集中在合成氯化金（I）配合物[（NHC）AuCl]上，并研究了用乙炔化物取代氯配体以获得相应的[（NHC）AuC≡CR]配合物。然后使用聚乙炔化物来获得卟啉仅与一个NHC配体稠合的分子多卟啉体系，而使用Janus卟啉双（NHC）时则得到主链有机金属聚合物（MCOP）。有趣的是，事实证明，包含锌（II）卟啉的MCOP作为可见光照射下产生单线态氧的多相光催化剂是有效的。
