Controlling the Crystallographic Packing Modes of Pt1Ag28 Nanoclusters: Effects on the Optical Properties and Nitrogen Adsorption-Desorption Performances.

We herein report the manipulation of the crystallographic packing modes of Pt1Ag28(S-Adm)18(PPh3)4 nanoclusters by altering counterions as different polyoxometalates (POMs). Specifically, the Cl- anion of the presynthesized Pt1Ag28 nanocluster was substituted by POM anions including [Mo6O19]2-, [W6O19]2-, or [PW12O40]3-. The crystal lattices of these Pt1Ag28 nanoclusters with diverse anions showed distinct packing modes and thus manifested remarkably distinguishable crystalline-state optical properties and nitrogen adsorption-desorption performances. Overall, the combination of intercluster control in this work and intracluster control reported previously (the control over metal-ligand within the nanocluster framework) accomplished a more comprehensive manipulation over the M29(SR)18(PR'3)4 nanocluster system, which enables us to further grasp the structure-property correlations at the atomic level.