Self-Assembly of Multinuclear Sandwich Silver(I) Complexes by Cooperation of Hexakis(azaheteroaryl)benzene Ligands, Argentophilic Interactions, and Fluoride Inclusion

Abstract

Self-assembly of AgOTf and AgF with the hexatopic ligands hexakis(pyridin-2-yl)benzene (2) and 2,4,6-tris(pyridin-2yl)-1,3,5-tris(quinolin-2-yl)benzene (3) affords the discrete sandwich-shaped complexes [Ag 4 F(2) 2 ](OTf) 3 , [Ag 4 F(3) 2 ]-(OTf) 3 , and [Ag 5 F(2) 2 ](OTf) 4 . The solid-state structures of the complexes were characterized by single-crystal X-ray diffraction analysis, which revealed that the fluoride anion is coordinated in the center of the Ag 4 -square or Ag 5 -pentagon units which are positioned between two molecules of the hexakis(azaheteroaryl)benzene. The generation of complexes is dictated by a unique cooperation of ligand coordination, argentophilicity, and fluoride anion inclusion. All three complexes adopt highly symmetrical structures in solution, as evidenced by appearance of one set of proton resonances for the two ligands arranged face to face.

Double Rotors with Fluxional Axles: Domino Rotation and Azide–Alkyne Huisgen Cycloaddition Catalysis

“…While fluxional molecules involving bond cleavage/formation have a long‐standing history, related dynamics within multiple degenerate structures in supramolecular multicomponent devices is scarce . Herein, for the first time, multicomponent rotors are equipped with fluxional axles allowing them to undergo domino rotation.…”

A Novel Tetranuclear Silver Compound with bis(3,5-dimethylpyrazol-1-yl)acetate: a Simple Synthesis Yielding Complex Crystal Structure

“…Additionally, Ag2 and Ag2' are bridged by two carboxylate bridges, bringing both atoms to the distance of 2.9062(4) Å which represents very strong argentophilic interaction. 34,35 Although the tetrasilver compounds are frequent in coordination chemistry of silver(I), such tetrasilver cluster Ag 4 O 6 N 8 as found in the title compound has not been observed yet. 9 The same holds true for the presence of tetradentately and tridentately coordinated bdmpza ligand: to the best of our knowledge, the title compound is the first that contains bdmpza ligands ligated in both manners to the metal centre.…”

Doppelrotoren mit fluktuierenden Achsen: Domino‐Rotation und Katalyse der Azid‐Alkin‐Huisgen‐Cycloaddition

“…Während fluktuierende Moleküle mit Bindungsspaltung/‐bildung eine lange Geschichte aufweisen, ist eine ähnliche Dynamik innerhalb multipler entarteter Strukturen in supramolekularen Mehrkomponentengeräten selten . Erstmals werden hier Mehrkomponentenrotoren mit fluktuierenden Achsen ausgestattet, die eine Domino‐Rotation ermöglichen.…”