Stacking angles played a decisive role in the coupling strength of the excited state, the overlap of electronic orbitals, and behavior of excitons, which further have ultimately affected the luminescent properties. However, developing effective strategies to precisely tailor molecular stacking anglets of chromophores still remains challenges. In this work, we constructed a series of figure-eight supramolecules S1–S3 through the coordination-driven self-assembly of anthracene-based 180° di-platinum(II) acceptor L and ditopic pyridyl ligands L1–L3, respectively. Variation in ligand length enabled regulation of intramolecular anthracene stacking angles in the assembled structures and photoluminescent properties. Photophysical studies revealed that larger stacking angles significantly enhance fluorescent intensities and photoluminescence quantum yields in both solution and solid states. Femtosecond transient absorption spectroscopy further demonstrated that the excited-state lifetimes of S1–S3 were extended due to suppressed non-radiative decay pathways. Moreover, density functional theory calculations showed that the increasing stacking angles weakened intramolecular anthracene interactions, leading to enhanced radiative transition rates. This study elucidated the relationship of molecular packing and luminescent properties, which will pave the way for construction of materials with excellent luminescent performance.
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