Counterion Effect and Isostructurality in a Series of Ag(I) Complexes Containing a Flexible, Imidazole Based Dipodal Ligand

The crystal structures of a series of Ag(I) complexes with 1,3-bis(imidazol-1-ylmethyl)-5-methylbenzene (L) and the counterions BF4− (1), PF6− (2), ClO4− (3), and CF3SO3− (4) were analysed to determine the effect of the latter on their formation. All resulting compounds crystallise in the non-centrosymmetric space group Cc of a monoclinic system and show the formation of cationic, polymeric 1D Ag(I) complexes. SCXRD analyses revealed that compounds 1–3 are isostructural, though 1 shows opposite handedness compared to 2 and 3, resulting in an inversed packing arrangement. The presence of the larger, elongated triflate counterion in 4 leads to a different ligand conformation, as well as different arrangements of the ligand in the cationic chain, and simultaneously results in a packing that exhibits fewer similarities with the remaining three compounds.

Counterion effect on sulfonatocalix[n]arene recognition

Sulfonatocalixarenes, like other ionic receptors, possess counterions that can affect the molecular recognition process. In the present review it is shown that the competitive effect of the alkaline cations frequently used as counterions determines not only the magnitude of the external guest association constant, but also the stoichiometry of the complexes. Experimental evidences are shown about the interaction of the counterions with sulfonatocalixarene, allowing to quantify its association equilibrium constants. The counterions recognition will be a competitive process that must be taken into account when investigating the interaction of calixarenes with an external guests. When the external guest is a neutral molecule it will be possible to form ternary complexes where the counterion shows a competitive and cooperative effect. By increasing the size of the receptor, sulfonatocalix[6] and sulfonatocalix[8]arene, the complexity of the system is increased due to the formation of counterion complexes with stoichiometries 1:1 and 1:2. In the presence of an external guest, the formation of heteroternary complexes with 1:1:1 stoichiometries including a counterion and an organic cation will be possible.