Abstract
AbstractThree metallosupramolecular assemblies composed of two bis‐NHCs and two silver atoms, [4](PF6)2, two tetra‐NHCs and four silver atoms, [7](PF6)4, and two tri‐NHCs and three silver atoms [8](BF4)3, have been prepared. Assemblies [4](PF6)2 and [7](PF6)4 feature NHC ligands decorated with terminal olefin groups. Irradiation of [4](PF6)2 yielded complex [5](PF6)2 with two terminal cyclobutane rings linking the two bis‐NHC ligands. Liberation of the macrocyclic tetrakisimidazolium salt H4‐6(PF6)4 was achieved by reaction of [5](PF6)2 with NH4Cl/NH4PF6. No [2+2] cycloaddition was observed upon irradiation of [7](PF6)4, apparently due to an unfavorable orientation of the olefin groups. Irradiation of complex [8](BF4)3 with three internal pairs of olefin groups leads to [9](BF4)3 as a mixture of two isomers that differ on the relative orientation of the internal cyclobutane rings. Reaction of [9](BF4)3 with NH4Cl/NH4BF4 yields an isomer mixture of the novel cage‐line hexakisimidazolium salt H6‐10(BF4)6.
Highlights
Over the last three decades, research on supramolecular coordination complexes (SCCs)[1] has emerged as an important sub-discipline of coordination chemistry
The post-assembly modification (PAM) methodology may constitute a valuable approach for the preparation of poly-imidazolium salts as anion receptors with enhanced binding affinities, as suggested by Jin and co-workers.[14d]. Our first progress in this area was recently described with the template-controlled preparation of an oktakisimidazolium salt starting from a tetrakisimidazolium salt.[14a]. The oktakisimidazolium salt turned out to be an efficient multivalent anion receptor with a binding affinity significantly larger than that shown by the original tetrakisimidazolium salt
New bis- and tetrakisimidazolium salts with terminal olefins and a trisimidazolium salt with internal olefins have been prepared and used for the synthesis of di, tetra- and trinuclear silver-NHC assemblies
Summary
Part of the “RSEQ-GEQO Prize Winners” Special Collection. have been mainly constructed from O-, N-, and P-donor Werner-type polydentate ligands. The PAM methodology may constitute a valuable approach for the preparation of poly-imidazolium salts as anion receptors with enhanced binding affinities, as suggested by Jin and co-workers.[14d] Our first progress in this area was recently described with the template-controlled preparation of an oktakisimidazolium salt starting from a tetrakisimidazolium salt.[14a] The oktakisimidazolium salt turned out to be an efficient multivalent anion receptor with a binding affinity significantly larger than that shown by the original tetrakisimidazolium salt Based on these previous findings, we describe here the preparation and characterization of a series of metallosupramolecular assemblies from poly-imidazolium salts featuring terminal or internal olefins and AgI ions. Demetallation of the poly-NHC complexes yielded novel poly-imidazolium salts not accessible by conventional organic synthesis
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