Mole-Ratio-Dependent Reversible Transformation between 2:2 and Cyclic 3:6 Silver(I) Complexes with an Argentivorous Molecule.

A tetra-armed cyclen () with two substituted 3,5-difluorobenzyl and two substituted pyridine-4-yl methyl groups at the 1,4- and 7,10-positions of the cyclen ring as side arms was synthesized. When was reacted with 1 equiv of the silver(I), dimetallo[3.3]paracyclophane-like 2:2 cyclic dimer, [Ag()](PF), was obtained.

Pentacyclic Nano-Trefoil.

Tetra-armed cyclen (1) bearing two 4-(4'-pyridyl)benzyl and two 3,5-difluorobenzyl groups and its Ag complexes were prepared and structurally characterized. The complexes formed between 1 and Ag undergoes a reversible structural transformation between a 2:2 dimeric complex and a 3:5 pentacyclic trefoil complex with changes in the Ag /1 molar ratio. It was also revealed that the 3:5 trefoil complex could encapsulate benzene and [D ]benzene selectively in solid-state.