01752nas a2200181   4500008004100000022001400041245008300055210006900138260000900207300001400216490000800230520115100238100002101389700002101410700002701431700001701458856009501475       2020                        eng d  a1089-563900aUnraveling the hidden role of the counteranion in ``cation in a cage'' systems0 aUnraveling the hidden role of the counteranion in cation in a ca  cOCT   a8040-80490 v1243 a<p>The current work showcases general principles at play in systems consisting of cations present inside molecular cages. Such systems, relevant to chemistry and biology, have been carefully investigated by computational methods. The important Ge(II)-encapsulating cage systems have been studied first. The very fact that such compounds exist appears highly unlikely, given the highly reactive nature of the Ge(II) dication. Our studies reveal what really occurs in solution when such complexes are formed: the Ge(II) dications are actually present as [Ge-X](+) (where X is the ``non-coordinating'' counterion employed in such systems) during entry and subsequent existence at the center of the cage. Hence, what is actually present is a ``pseudomonocation''. Interestingly, such pseudomonocation-encapsulated cages are seen to be equally relevant in systems of biological importance, such as for dicationic s block-based ionophores. In explaining such cases, the concept of ``isoionicity'' is introduced, demonstrating that the counterion-coordinated dications are isoionic with a monocation, such as Li(I), isolated in the same ionophore.</p>
1 aMukherjee, Anagh1 aGhule, Siddharth1 aTiwari, Mrityunjay, K.1 aVanka, Kumar  uhttps://library.ncl.res.in/content/unraveling-hidden-role-counteranion-cation-cage-systems