在三脚架配合物中利用吡唑氢键形成自组装同手性二聚体。

Brewer Greg, Butcher Raymond J, Zavalij Peter

Department of Chemistry, Catholic University, Washington, DC 20064, USA.

Department of Chemistry, Howard University, Washington, DC 20059, USA.

Materials (Basel). 2020 Mar 31;13(7):1595. doi: 10.3390/ma13071595.

The 3:1 condensation of 5-methyl-1H-pyrazole-3-carboxaldehyde (MepyrzH) with tris(2-aminoethyl)amine (tren) gives the tripodal ligand tren(MePyrzH). Aerial oxidation of a solution of cobalt(II) with this ligand in the presence of base results in the isolation of the insoluble Co(tren)(MePyrz) This complex reacts with acids, HCl/NaClO, NHClO, NHBF, and NHI to give the crystalline compounds Co(tren)(MePyrzH)(ClO), {Co(tren)(MePyrzH)} {Co(tren)(MePyrzH)} and [Co(tren)(MePyrzH)][Co(tren)(MePyrzH)]I The latter three complexes are dimeric, held together by three N -HN hydrogen bonds. The structures and symmetries of these homochiral dimers or pseudodimers are discussed in terms of their space group. Possible applications of these complexes by incorporation into new materials are mentioned.

5-甲基-1H-吡唑-3-甲醛（MepyrzH）与三（2-氨基乙基）胺（tren）以3:1缩合得到三脚架配体tren(MePyrzH)。在碱存在下，钴（II）溶液与该配体进行空气氧化反应，得到不溶性的Co(tren)(MePyrz)。该配合物与酸HCl/NaClO、NH₄ClO₄、NH₄BF₄和NH₄I反应，生成晶体化合物Co(tren)(MePyrzH)(ClO₄)、{Co(tren)(MePyrzH)}₂、{Co(tren)(MePyrzH)}₂和[Co(tren)(MePyrzH)]₂[Co(tren)(MePyrzH)]I₂。后三种配合物是二聚体，通过三个N-H···N氢键结合在一起。根据它们的空间群讨论了这些手性纯二聚体或假二聚体的结构和对称性。还提到了将这些配合物掺入新材料中的可能应用。