Cocrystallization of Atomically Precise Nanoclusters

Abstract

Of the great classes of nanocluster crystallization, "cocrystallization" has gained significant attention due to its elucidation of both intracluster structures and intercluster packing modes. In addition, the intermolecular interactions and resulting assembled constructs endow the cocrystallized materials with novel physical and chemical properties that differ from those of the individual components. Heterogeneous cocrystallization has recently emerged as a new "growth point" in nanocluster science. In this Perspective, we elaborate on relevant advances in studying the cocrystallization of metal nanoclusters. The packing patterns of the cocrystallized nanoclusters, as well as their geometric structures, are discussed case by case. In addition, the intercluster interactions among heterogeneous nanoclusters that account for the cocrystallization are also disclosed. The goal of this Perspective is to provide researchers attempting to study nanocluster cocrystallization with research fundamentals and to further propose some possible approaches (or new growth points) for the design and fabrication of cocrystallized cluster systems.

Small symmetry-breaking triggering large chiroptical responses of Ag70 nanoclusters

“…Aiming to further verify the above-proposed stability mechanism in solution, we attempted to prepare single crystals that contained an anionic Ag 70 cluster and a small Ag(I) 12 cluster ({Ag 12 (S i Pr) 6 (CF 3 COO) 6 }) as a stabilizer, which was named Ag 70 ·Ag 12 (Supplementary Figs. 41 – 57 ) 37 – 43 . The appearance of Ag(I) 12 cluster could be attributed to the remainder of the unreduced silver(I) fragments in the EtOH-DMF system.…”

Phosphorescent Metal Rotaxane-like Bimetallic Ag/Au Clusters

“…Similarly, the Ag 13– x Cu x –H clusters with 1 < x < 2 in our previous work are cocrystals of Ag 12 Cu–H and Ag 10 Cu 3 –H according to the SCXRD, ICP-AES, EDX, and EPMA analyses. Recently, Kang and Zhu summarized cocrystals consisting of different metal nanoclusters and highlighted the cocrystallization of heterogeneous nanoclusters as a new “growth point” in nanocluster science …”

“…Recently, Kang and Zhu summarized cocrystals consisting of different metal nanoclusters and highlighted the cocrystallization of heterogeneous nanoclusters as a new "growth point" in nanocluster science. 42 Computational studies using models based on their crystal structures confirm that the Au(I) locates at the center of the Au@Ag 12 core rather than on the outside (see the Supporting Information for details). The combination of spectroscopic and computational evidence suggests that the substituent effects play essential roles in the emission energies and colors of these bimetallic Au/Ag clusters.…”

Ligand Effects on Intramolecular Configuration, Intermolecular Packing, and Optical Properties of Metal Nanoclusters

“…Metal nanoclusters, bridging between small-sized molecular complexes and large-sized plasmonic nanoparticles, have attracted considerable attention owing to their atomically precise structures and excellent electrical, optical, and catalytical properties directed by the discrete electronic energy level as well as the structure-dependent quantum confinement effect [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 ]. The monodispersed sizes, precise compositions, and accurate configurations of metal nanoclusters make it possible to investigate the relationship between their structures and properties.…”