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The disentanglement of electron transfer from metal binding effects allowed their contributions to the overall core perturbation of the negatively-charged [8]CPP to be revealed. Consequently, the internal coordination of potassium cations is identified as the main driving force for drastic elliptic distortion of the macrocyclic framework upon reduction.Organic host-guest doped materials exhibiting the room temperature phosphorescence (RTP) phenomenon have attracted considerable attention. However, it is still challenging to investigate