HTBZ-HMA demonstrated the highest increase in TBZ solubility. The dissolution of HTBZ-HMA (neat) and HTBZ-HMA (LAG) resulted in a TBZ concentrations of 2.00(1) mg/ml (approximately 52-fold increase) and 2.28(17) mg/ml (approximately 60-fold increase), respectively. The significant enhancement in solubility can be attributed to the crystal structure and packing of HTBZ-HMA. Unlike the other structures studied, HTBZ cations in HTBZ-HMA do not form π-π stacked columns with each other. Instead, the columns have alternating HTBZ and HMA ions (Figure ). HMA exhibits a significantly weaker ability to engage in π-π interactions than electron-rich HTBZ cations. Consequently, this leads to less thermodynamically favorable packing and higher solubility.