In both systems, with further increasing the 3D ratios up to ~ 20%, much higher-n phases progressively emerge, and then the 3D-like HP phases become dominant when the 3D ratio exceeds ~30% (~25% for PEA), involving marginal amounts of lown 2D HPs. Similar phase emergence behaviors are also observed in BA-based system, which, however, starts at relatively higher 3D composition ratios of ~40%. This can also be explained by the retarded diffusion of the ThEA and PEA spacers. This subsequently slows down their surface coordination to the HP lattice, and such slower crystallization kinetics offers longer times for growth of inorganic lattice, thus manifesting thicker HPs. Similar crystallization mechanisms have been proposed for the quasi-2D HPs incorporating coordinative molecular additives in the precursor system (e.g., crown ethers, and so on), where their strong coordination actions to the inorganic lattice prevent the complete formation of 2D HPs .