Capture of Cesium Ions with Nanoclusters: Effects on Inter- and Intramolecular Assembly

The capture of cations with nanoclusters is a flourishing area in the nanocluster science due to their effects on both molecular chemistry and supramolecular chemistry. The capture of Cs + is most concerned in this field for its capability of controlling the synthesis and assembly of nanoclusters. However, the atomically precise interaction between Cs + ions and nanoclusters remains mysterious. In this paper, we report the first X-ray crystal structure of a Cs + -captured nanocluster, formulated as Cs 3 Ag 29 (SSR) 12 (DMF) x ( x = 5, 6; SSR, 1,3-benzene dithiol). The capture of Cs + with Ag 29 (SSR) 12 (PPh 3 ) 4 peels the PPh 3 ligands off from the nanocluster surface, giving rise to Cs 3 Ag 29 (SSR) 12 (DMF) x . The Cs + –cluster interactions not only alter the geometric structure of the Ag 29 (SSR) 12 kernel but also assemble Ag 29 (SSR) 12 clusters into one-dimensional, cluster-based lines. Remarkable differences have been observed by comparing the optical properties of the Cs 3 Ag 29 (SSR) 12 (DMF) x nanocluster in solutions or in crystallized films. Overall, this work is of great significance for revealing both the Cs + -induced intracluster transformation of nanocluster structures and the Cs + -induced intercluster self-assembly.