A series of thiosemicarbazonato-hydrazinatopyridine zinc(II) complexes were evaluated as direct air CO2 capture agents. The complexes sequester CO2 in a methanol solution as a metal-coordinated methylcarbonate. The reaction is reversible upon sparging of solutions with an inert gas (N2 or Ar). The capture process involves metal-ligand cooperativity with the noncoordinating nitrogen of the hydrazinatopyridine functional group serving as a Brønsted-Lowry base and the zinc acting as a Lewis acid. In this study, the pendent amine of the thiosemicarbazonato group was varied to include 4-phenyl (ZnL5), 4-(trifluoromethyl)phenyl (ZnL6), 4-cyanophenyl (ZnL7), 4-tolyl (ZnL8), and 4-naphthyl (ZnL9). Hyperconjugation between the pendent group and the ligand core resulted in modulation of the metal ion acidity, as quantified by ligand exchange equilibrium constants (K3 = 193-511) and ligand basicity (pKa,MeOH = 11.09-11.94). Variations in electronic structure that decreased ligand basicity were more than offset by increases in Lewis acidity. The equilibrium constant (K1) for CO2 capture varied from 46300 to 73700. Overall, the value of K1 was directly related to the relative Lewis acidity of the complexes (K3). Notably, there was an overall inverse relationship between K1 and the ligand basicity. The results provide insights into ligand design to further improve CO2 capture.