Collision-induced dissociation (CID), along with infrared multiple photon dissociation/detachment (IRMPD) techniques, is utilized to study a series of doubly substituted aromatic dianions containing sulfonate and carboxylate functionalities (1,2- and 1,3-benzenedisulfonate, 1,5-naphthalenedisulfonate, 2,6-naphthalenedisulfonate, 4-sulfobenzoate, 2,6-naphthalenedicarboxylate, and terephthalate dianions). The molecules were chosen because of the electronegativity of the CO(2) and SO(3) moieties along with their varied spatial separation in order to investigate the effect of the repulsive Coulomb barrier (RCB) on the dianions' respective dissociation pathways. Density functional theory calculations of the structures, electron detachment and dissociation energies, as well as vibrational frequencies are performed. Calculated infrared active vibrational frequencies are largely in agreement with the IRMPD spectra which provide support for interpretations based upon computed energies. Calculated and experimental results show that fragmentation dominates over electron detachment as the lowest energy dissociation pathway for these systems and the nature of this dissociation is dictated by properties of the substituent group. CID and IRMPD of dianions with two sulfonate groups (SO(3)(-)) resulted in a single dissociation channel leading to observation of SO(3)(-) and its anion conjugate pair, whereas the carboxylate (CO(2)(-)) containing dianions dissociated via loss of one or both CO(2) molecules and an electron. The SO(3)(-) collisional dissociation exhibited a clear energetic threshold toward ionic fragmentation with an isomeric dependence that is in reasonable agreement with a simple electrostatic model of the RCB, as well as with published reports on electron photodetachment. The loss of one or both CO(2) units and an electron from CID of the carboxylate dianions appeared with no threshold (dissociation occurs with no collision gas), implying these dianions to be metastable toward the dissociation pathway. However, calculations show these ions to be energetically stable toward dissociation as well as electron detachment. More importantly, in the case of the 2,6-naphthalenedicarboxylate dianion, experiments performed at the FELIX Fourier-transform ion cyclotron resonance facility and the ELISA electrostatic storage ring, where ions are collisionally cooled prior to analysis, showed this ion to be stable (tau>1.5 s). We conclude that the carboxylate (CO(2)(-)) containing dianions formed in the present CID experiment are electronically stable but vibrationally metastable due to internal energy imparted in the harsh electrospray conditions. The delocalized nature of the excess electrons associated with the carboxylate containing dianions may lead to circumvention of the RCB by dissociating via neutral fragmentation followed by (or accompanied by) electron detachment.