Negative ion photoelectron spectra at 20 K along with ab initio [CCSD(T)] and M06-2X density functional theory calculations are reported for a series of six basic and nucleophilic pyridine derivatives with an anionic substituent [i.e., 3- and 4-PyrBX3-, where X = F, 4-t-BuC6H4, 4-MeOC6H4, and 3,5-(MeO)2C6H3]. Vertical detachment energies (VDEs) of these charge-activated reagents span from 4.50-5.85 eV and are well reproduced by M06-2X/aug-cc-pVTZ and CCSD(T)/maug-cc-pVTZ computations. Surprisingly, the VDEs are found to correlate with the SN2 reactivity of the PPh4+ salts of the substituted pyridine anions with 1-iodooctane in dichloromethane. This provides an experimental measure of the nucleophilicity of these charge-activated anions, which represent a new class of chemical reagent.