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Tiara-like thiolated group 10 transition metal (Ni, Pd, Pt) nanoclusters have attracted extensive interest due to their fundamental scientific significance and potential application in a number of fields. However, the properties (e.g. the absorption) evolution with the ring size's increase was not investigated so far to our best knowledge, due to the challenge of obtaining a series of nanocluster analogues. Herein, we successfully synthesized, isolated and identified a family of [Pd(SC2H4Ph)2]n nanoclusters (totally 17 novel clusters, n = 4-20). Their structures were determined to be tiara-like by single crystal X-ray crystallography together with theoretical calculation; their formation mechanism was proposed to be a substitution-polycondensation-ring-closure process based on experimental observations. All of these clusters are rather robust (anti-reductive and anti-oxidative) owing to their tiara-like structures with large HOMO-LUMO gaps. Finally, the optical and electrochemical evolution with the increase of ring size was investigated, and it is found that both optical and electrochemical gaps have a 'turning point' at a size corresponding to n = 8 for [Pd(SR)2]n nanoclusters. [ABSTRACT FROM AUTHOR]