Octahedral vs Tiara-like Pd₆(SR)₁₂ Clusters

Atomically precise Pd-thiolate clusters are well-known for their well-defined structures and diverse applications involving catalysis, sensors, and biomedicine. While many of these clusters have been studied, their molecular structures typically feature a tiara-like arrangement. In this study, we present the first example of a non-tiara-like Pd-thiolate cluster: the octahedral Pd6(SC6H11)12 (denoted as Pd6-Oct). The composition and geometric structure of the cluster were characterized using electrospray ionization mass spectrometry (ESI-MS) together with single-crystal X-ray diffraction (SXRD). Despite having a similar chemical composition to tiara-like Pd6(SC2H4Ph)12 (denoted as Pd6-Tia), Pd6-Oct exhibits a distinctly different geometric structure. Additionally, UV–vis–NIR absorption spectroscopy combined with quantum chemical calculations provided valuable insights into the electronic structures of these clusters. The excited-state dynamics, host–guest chemistry, and the catalytic properties of Pd6-Oct and Pd6-Tia were examined to compare their structure–property relationships. This research represents significant advances in the synthesis and understanding of structure–property correlations in Pd-thiolate clusters.