Octahedral vs Tiara-like Pd<sub>6</sub>(SR)<sub>12</sub> Clusters.

Ruan, Chenhao; Meng, Changqing; Wang, Kunpeng; Li, Yanshuang; Xiang, Huixin; Yan, Hao; Xu, Wen Wu; Zhou, Meng et al. · Nano Lett · 2024

basic_science · Level V

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Abstract

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 Pd<sub>6</sub>(SC<sub>6</sub>H<sub>11</sub>)<sub>12</sub> (denoted as Pd<sub>6</sub>-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 Pd<sub>6</sub>(SC<sub>2</sub>H<sub>4</sub>Ph)<sub>12</sub> (denoted as Pd<sub>6</sub>-Tia), Pd<sub>6</sub>-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 Pd<sub>6</sub>-Oct and Pd<sub>6</sub>-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.