Sodium Cationization Enables Exotic Deprotonation Sites on Gaseous Mononucleotides

We report observation and photoelectron spectroscopic characterization of sodium cationization on four doubly deprotonated mononucleotide dianions Na⁺·[dNMP-2H]^2- (N = A, G, C, or T) in the gas phase. Multiple tautomers with distinct deprotonated sites are identified, in which Na⁺ enables novel double deprotonation patterns and folds the resultant mononucleotide dianions. The most stable isomer for the whole family is derived from detaching one proton from the phosphate and the other from the nucleobase (amino group for N = A, G, and C, but nitrogen atom for T), whereas high-lying isomers with protons detached separately from the phosphate and the hydroxy group of sugar coexist. Particularly, an exotic deprotomer with both protons deprived from guanosine is populated as well. This work thus displays a remarkably diverse binding landscape enabled by sodium cationization, a potentially critical element in developing a general formulism to better model metal cation and nucleotide interactions.