These multimacrocycles were fully characterized by NMR spectroscopy and highresolution mass spectrometry (HRMS) after standard workup and purification. The crown ether units within the macrocyclic backbone facilitated clear detection of sodium and potassium ion association in the mass spectra (Scheme 1b). Compared to bismacrocycle 6, trimacrocycle 7 features two identical [8]CPP units flanking the dibenzo-24-crown-8 core, enhancing molecular symmetry, as confirmed by its 1 H NMR spectrum (Scheme 1c). Single crystals of 6 were prepared by slow diffusion of diisopropyl ether into toluene solution. As shown in Figure (left), the structure of 6 can be recognized as an integration of the two classic macrocycles, dibenzo-24-crown-8 and [8]CPP. The two independent cavities do not overlap with each other, the distance between the two phenyl rings of dibenzo-24-crown-8 and the diameter of [8]CPP are calculated to be 10.5 Å and 10.4 Å, respectively. Then, we dissolved equimolar amounts of compounds 6 and KPF6 in a 1:1 CHCl3-MeOH solution and obtained single crystals of the metal complex 6K + through slow evaporation of the CHCl3. Analyzing the X-ray crystal structure of complex 6K + , we can see that the 24-crown-8 ring tightly encapsulates the potassium ion by folding, primarily via multiple electrostatic interactions, the average distance of OK is 2.5 Å (Figure , right). Due to the introduction of the 24crown-8 ring, [8]CPP no longer presents ordered columnar packing, 10 but a random packing with no apparent supramolecular interactions between the complex molecules was found in the solid state (Figure and). This also leads to 6 having better solubility in organic solvents. closely resemble that of [8]CPP, exhibiting a primary absorption maximum around 335 nm and a shoulder near 400 nm, attributed to the HOMO → LUMO transition. The molar extinction coefficient (ε) at 335 nm for 6 (8.510 4 M -1 cm -1 ) is comparable to that of [8]CPP, whereas 7 (1.310 5 M -1 cm -1 ) exhibits approximately 1.5 times higher absorption. This increase suggests that the two CPP units in 7 behave as independent chromophores, consistent with Beer's Law, although possible excitonic coupling effects cannot be ruled out.