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Towards electron encapsulation. Polynitrile approach

Is it possible to design a supramolecular cage that would "solvate" the excess electron in the same fashion in which several solvent molecules do that co-operatively in polar liquids? Two general strategies are outlined for "electron encapsulation," viz. electron localization using polar groups arranged on the (i) inside of the cage or (ii) outside of the cage. The second approach is limited to polynitriles. We demonstrate that the latter faces a formidable problem: the electron attaches to the nitrile groups forming molecular anions with bent C-C-N fragments. Since the energy cost of this bending is very high, for dinitrile anions in n-hexane, the binding energies for the electron are very low and for mononitriles, these binding energies are lower still, and the entropy of electron attachment is anomalously small. Density functional theory modeling of electron trapping by mononitriles in n-hexane suggests that the mononitrile molecules substitute for the solvent molecules at the electron cavity, "solvating" the electron by their methyl groups. Such "solvated electrons" resemble multimer radical anions in which the electron density is shared (mainly) between C 2p orbitals in the solute/solvent molecules, instead of existing as cavity electrons. The way in which the excess electron density is shared by such molecules is similar to the way in which this sharing occurs in large di- and poly- nitrile anions, such as 1,2,4,5,7,8,10,11-octacyano-cyclododecane anion. The work thus reveals limitations of the concept of "solvated electron" for organic liquids. It also demostrates the feasibility of "electron encapsulation."