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Synthesis, Characterization, and Properties of Organometallic Molecular Cylinders Bearing Bulky Imidazo[1,5‐ a ]pyridine‐Based N‐Heterocyclic Carbene Ligands
Author(s) -
Zhang YaWen,
Das Rajorshi,
Li Yang,
Wang YaoYu,
Han YingFeng
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201806204
Subject(s) - tetrahydrothiophene , transmetalation , chemistry , pyridinium , carbene , pyridine , supramolecular chemistry , molecule , organometallic chemistry , group 2 organometallic chemistry , stereochemistry , yield (engineering) , metal , crystallography , polymer chemistry , medicinal chemistry , organic chemistry , materials science , crystal structure , catalysis , metallurgy
The metal‐controlled self‐assembly of organometallic molecular cylinders from a series of imidazo[1,5‐ a ]pyridine‐based tris‐NHC ligands is described in this report. The imidazo[1,5‐ a ]pyridinium salts H 3 ‐ L (PF 6 ) 3 ( L = 4 a – 4 c ) were treated with 1.5 equivalents of Ag 2 O to yield the trinuclear Ag I hexacarbene cages [Ag 3 ( L ) 2 ](PF 6 ) 3 ( L = 4 a – 4 c ), in which three Ag I are sandwiched between the two tricarbene ligands. The silver(I) complexes [Ag 3 ( L ) 2 ](PF 6 ) 3 underwent a facile transmetalation reaction in the presence of 3 equivalents of [AuCl(tht)] (tht=tetrahydrothiophene) to furnish the trinuclear Au I cylinder‐like cages [Au 3 ( L ) 2 ](PF 6 ) 3 ( L = 4 a – 4 c ) without destruction of the metallosupramolecular structure. The new hexacarbene assemblies feature a large cavity that can easily accommodate a molecule of dimethyl sulfoxide as molecular guest. This is the first study of a unique “host–guest” system containing an organometallic cylinder‐like cage derived exclusively from poly‐NHC ligands.