Enhanced J -Couplings through Specially Solvated Electron in Perfluoro-[ n ]Prismanes and [ n ]Asteranes.

Perfluoro-[ n ]prismanes ((C 2 F 2 ) n , n = 3-8) and [ n ]asteranes ((C 3 F 4 ) n , n = 3-5) exhibit a strong perfluoro cage effect that can stably encapsulate an additional electron inside the cage. The 2s-like distribution of solvated electron (e sol - ) not only changes the molecular structure but also affects the nuclear spin properties. In this work, we reveal how the e sol - enhances and regulates indirect nuclear spin-spin coupling between two coupled F nuclei ( J FF -coupling). Results show that e sol - is mainly distributed in the central cavity, and a part of it penetrates into the C-shell and C-F bond regions due to the unique polyhedral C-shell structure. Such a 2s-like e sol - creates a novel e sol - based coupling mechanism, including the newly generated through-e sol - (TSE) and e sol - -enhanced traditional through-bonds and through-space (e sol - -enhanced TB+TS) pathways, enhancing and regulating N (e) J FF -coupling, which crosses N bonds in the shortest TB pathway and is affected by e sol - . The contribution of the TSE ( J TSE ) is positive and increases with the increase of the central angle between two coupled F nuclei (∠F⊗F), and the contribution of the e sol - -enhanced TB+TS ( J TB+TS ) is negative and | J TB+TS | decreases with the increase of N and straight linear distance between two coupled F nuclei ( d FF ). Interestingly, N (e) J FF exhibits a special dependence on N / d FF and ∠F⊗F due to the cooperation and competition between J TSE and J TB+TS . When ∠F⊗F < 70°, the e sol - -enhanced TB+TS can play a role; J TB+TS determines sign and magnitude of N (e) J FF . When ∠F⊗F > 70°, the TSE dominates, and J TSE determines sign and magnitude of N (e) J FF . This work not only further enriches information on the states, distributions, and properties of e sol - but also provides insights into the nuclei spin properties in perfluorinated polyhedrons triggered by e sol - .