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Here, the observation of spin-polarized emission for the Au25 (SC8 H9 )18 monolayer-protected cluster (MPC) is reported. Variable-temperature variable-field magnetic circular photoluminescence (VTV H ⇀ -MCPL) measurements are combined with VT-PL spectroscopy to provide state-resolved characterization of the transient electronic structure and spin-polarized electron-hole recombination dynamics of Au25 (SC8 H9 )18 . Through analysis of VTV H ⇀ -MCPL measurements, a low energy (1.64 eV) emission peak is assigned to intraband relaxation betwee
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