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Our studies uncover new roles for neutral donor ligands in stereospecific ROP, including suppression of chain-scission events, and point to new opportunities for catalyst design.Understanding the origin and structural basis of the photoluminescence (PL) phenomenon in thiolate-protected metal nanoclusters is of paramount importance for both fundamental science and practical applications. It remains a major challenge to correlate the PL properties with the atomic-level structure due to the complex interplay of the metal core (i.e. the inner kernel) and the ex