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C 3 ‐Symmetric Assemblies from Trigonal Polycarbene Ligands and M I Ions for the Synthesis of Three‐Dimensional Polyimidazolium Cations
Author(s) -
Zhang Le,
Das Rajorshi,
Li ChangTao,
Wang YaoYu,
Hahn F. Ekkehardt,
Hua Kai,
Sun LiYing,
Han YingFeng
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201907003
Subject(s) - trigonal crystal system , ligand (biochemistry) , chemistry , crystallography , metal , stereochemistry , trigonal prismatic molecular geometry , metal ions in aqueous solution , ion , cycloaddition , trigonal pyramidal molecular geometry , medicinal chemistry , crystal structure , catalysis , organic chemistry , octahedron , receptor , biochemistry
Metallosupramolecular poly‐NHC‐metal assemblies were prepared from trigonal hexakis (H 6 ‐ 1 a (PF 6 ) 6 and H 6 ‐ 1 b (PF 6 ) 6 ) or nonakis (H 9 ‐ 3 (BF 4 ) 9 ) imidazolium salts and Ag 2 O. Complexes [Ag 6 ( 1 a ) 2 ](PF 6 ) 6 and [Ag 6 ( 1 b ) 2 ](PF 6 ) 6 are built from six Ag + ions sandwiched between two trigonal hexacarbene ligands with an inner and an outer NHC donor in each of the three ligand arms. The metal atoms are arranged in two triangles. The hexakis‐NHC ligands bear cinnamic ester groups at the outlying NHC donors, used in postsynthetic [2+2] cycloaddition reactions linking two hexakis‐NHC ligands by three cyclobutane units to give complexes [Ag 6 ( 2 a )](PF 6 ) 6 and [Ag 6 ( 2 b )](PF 6 ) 6 bearing a dodecacarbene ligand. From the related nonakisimidazolium salt H 9 ‐ 3 (BF 4 ) 9 , complex [Ag 9 ( 4 )](BF 4 ) 9 bearing an octadecacarbene ligand was obtained. Removal of the template metals yielded very large, stable, polyimidazolium cations with 12 or 18 internal imidazolium groups.