In dichloromethane at 298 K, 6 and 7 display fluorescence emission bands centered at 525 nm and 530 nm, respectively, upon excitation at 340 nm (Figure ). Compared to [8]CPP, these multimacrocycles exhibit a slight blue shift, which may arise from subtle structural distortions induced by the crown ether ring. Such distortions could slightly reduce effective π-conjugation, thereby increasing the energy gap between the excited and ground states. More notably, their fluorescence quantum yields ( = 0.58 for 6, 0.60 for 7) are significantly higher than that of [8]CPP ( = 0.10) , indicating a strong enhancement in radiative emission efficiency. The fluorescence enhancement can be attributed to multiple factors. First, orbital symmetry breaking in the CPP backbone may increase the transition dipole moment, thereby enhancing radiative decay rates (Figure ). Second, the introduction of crown ether moieties may impose structural rigidity, reducing non-radiative relaxation pathways such as intramolecular rotations or vibrations. Time-resolved fluorescence measurements reveal that the fluorescence lifetimes of 6 (2.8 ns) and 7 (4.3 ns) are comparable to that of [8]CPP, suggesting that the increased fluorescence quantum yield is primarily due to suppression of non-radiative decay rather than an intrinsic increase in excited-state lifetime. In the solid state, 6 and 7 maintain  values of 14% and 18%, respectively, despite the potential for aggregation-caused quenching (ACQ). This suggests that the presence of crown ether substituents helps mitigate intermolecular π-π stacking, likely by introducing steric hindrance and restricting molecular aggregation. Guest Recognition. Analysis of the X-ray crystal structure of 6 revealed that the flexible crown ether backbone adopts a folded conformation. This structural feature led us to hypothesize that trimacrocycle 7 might serve as an effective host for fullerene recognition. While [10]CPP is well known for encapsulating C60 via strong π-π interactions, the smaller size of [8]CPP generally results in weaker binding. Given the structural modifications introduced in 7, we sought to evaluate its binding properties toward C60 through fluorescence quenching titrations in toluene. The binding study revealed that 6⊃C60 forms with an association constant (KA = 1.510 -5 M -1 , Figure ), which is significantly lower than [10]CPP⊃C60 (3.610 -6 M -1 ) 13 but higher than unmodified [8]CPP, likely due to additional dispersion interactions introduced by the crown ether side chains. In contrast, titration experiments between 7 and C60 exhibited a 1:2 (host : guest) binding equilibrium, with the first binding event showing a much higher association constant (K1:1 = 8.5  10 -5 M -1 , Figure ) compared to 6⊃C60. This suggests that 7 adopts a molecular tweezerlike conformation, where its two CPP units cooperatively encapsulate the fullerene, significantly enhancing its binding affinity. The second binding event occurs with a weaker association constant, likely due to steric hindrance and reduced π-π interactions when two fullerenes bind to a single host. DFT-optimized structures confirm that C60 sits symmetrically within the cavity of 7, stabilized primarily by dispersion forces between the π-conjugated CPP units and the fullerene surface. Independent Gradient Model (IGM) analysis further highlights strong non-covalent interactions in the 7⊃C60 complex, reinforcing the enhanced binding affinity observed experimentally.