For M2-I, a completely different self-assembly mode was adopted. As shown in Figure , six arms from each M2-I molecule engage with other arms from other M2-I molecules to form a perfect three-dimensional (3D) cubelike structure. Each M2-I molecule takes on the role of one of the square faces within the cubic assembly, reminiscent of the classic "Luban" lock depicted in Figure . Notably, the methylpyridine units on each arm of M2-I, functioning as hydrophilic ends, exhibit a propensity to aggregate, thus constituting the hydrophilic periphery of the resulting cube. Simultaneously, the iodide ions, serving as counter anions, arrange themselves along the external surface of the cube. The as-formed 3D cubes are then arranged along the a, b, and c-axis to form even bigger 3D cube-like self-assembled structures (Figure and). As we know, the specific supramolecular self-assembly process depends on several factors, including the internal structure of the monomers and the external environment. The self-assembly of both M1 and M2 takes place within a water environment under similar external conditions. Consequently, the inherent structures of the monomers play a pivotal role in governing the self-assembly process. The vinyl linkage in M2 results in different intermolecular interactions and thus affects their self-assembly behavior. The extended vinyl linkages provide M2 with certain rotational freedom and flexibility, thus causing the relatively flexible orientations of the six arms in M2 during the self-assembly process. Each arm from one M2 molecule meshes with another two arms from the other M2 molecules like gear to form the cube. The hydrophilic effect provides a main driving force for the formation of a hollow supramolecular cage. The methylpyridine groups as hydrophilic ends tend to stay together to realize the meshing process of the hydrophilic arms. An inner hydrophobic cavity was formed. Thus, the exposure of the hydrophobic core surface areas to the water was then minimized. M1 consisted of a series of short and rigid benzene rings, which limited the freedom of movement. An obvious π-π interaction between the headto-tail methylpyridine rings from adjacent M1 molecules was observed, leading to the 2D framework structures. This head-to-tail orientation can effectively minimize the Coulombic repulsive interactions between the methylpyridine cations. Notably, a large portion of counter anions was found to locate between the interlayer and the triangular pores. A large number of hydrogen bonds between the counter anions and the hydrogen of M1 formed, especially for the counter anions located between the interlayer. Therefore, the exchange of the counter anions from I -to Cl -induced the change of the stacking mode along the c-axis. The complementarity and synergy of the π-π interactions and the multiple hydrogen bonds lead to the 2D framework structure with diversified stacking.