The phase emergence behaviors in the aromatic RP spacers are also explored. ThEA and PEA exhibit similar phase emergence behaviors across compositional space, likely due to their similarity in molecular structure (Figure and, respectively). At low 3D ratios up to ~10%, n=1 and 2 2D HPs dominantly emerge in both systems. Meanwhile, weak PL signals associated with higher-n phases (n≥3) are also observed in the synthesized films. Comparatively, the PL emergences of these higher-n phases in both quasi-2D HP systems are weaker than those in the BA counterpart. Such discrepancy in the emergence of higher-n phases can be synergistically attributed to the heavier molecular weights of ThEA and PEA compared with BA, as well as the stronger inter-molecular interaction between the spacer cations through the aromatic rings in these molecules. The non-trivial π-π stacking behavior, together with their larger molar masses than that of BA, likely impedes the diffusion action in the precursor solution, thus restricting the formation of the kinetic products. Note that the emergence of high-n 2D HPs are more suppressed in PEA-based system compared to the ThEA counterpart, despite relatively lighter molecular weight of PEA. This suggest that inter-molecular interaction -particularly, the π-π stacking behavior -of PEA is stronger than that of ThEA.