Structural Isomerization in Cu(I) Clusters: Tracing the Cu Thermal Migration Paths and Unveiling the Structure-Dependent Photoluminescence

Abstract

Revealing structural isomerization in metal clusters would bridge huge structural gap between small molecular isomerization and solid-solid phase transformation. However, genuine structural isomerism in metal clusters is still rare. In this work, we report the first example of structural isomerism in Cu clusters. By utilizing the coordination flexibility of alkyne to enable the migration of partial Cu atoms in Cu metal cores, two Cu 15 cluster complexes (Cu 15 -a and Cu 15 -c) possessing identical composition but different metal core structures have been successfully isolated. Interestingly, although the structure of Cu 15 -a can keep retained in CH 2 Cl 2 solution below 27 °C, it will gradually change to give an intermediate state Cu 15 -b as the temperature rises (about 31 °C) before it eventually transforms into Cu 15 -c (40~65 °C). Significantly, atomic precise Cu 15 -b clearly provides insightful footprints for tracing thermal migration process of Cu atoms during the thermal-transformation from

Kernel Regulation of Ultra‐stable Cu12 Nanoclusters by Triple Collaborative Ligands

“…The effects of the ligand type (difference in substituent groups) on the electronic structure, stability, and function of Cu clusters have been investigated [34,35] . Given that the strength of metallophilic interaction is comparable to the hydrogen bond, the metal core of the Cu cluster is flexible regarding the commonly used protecting ligands such as thiolates and alkynes [36] . As results, most of these studies are carried out on Cu clusters with different kernel structures [3,36,37] .…”

“…[34,35] Given that the strength of metallophilic interaction is comparable to the hydrogen bond, the metal core of the Cu cluster is flexible regarding the commonly used protecting ligands such as thiolates and alkynes. [36] As results, most of these studies are carried out on Cu clusters with different kernel structures. [3,36,37] To obtain detailed information regarding ligand-directed properties, it is essential to synthesize Cu clusters with the same nuclearities but different kinds of ligands.…”

Predesigned Cluster-Based Spacers for Versatile Luminescent Metallacages

“…47−49 To overcome this issue, we conjure up a new strategy that combines the merits of CMCs and traditional metal nodes in metallacages: dual nodes for metallacages are expected to alleviate the stringent requirements of curvature of CMCs as nodes in whole-cage structure and to make use of the controllable coordination direction of traditional metal nodes. Considering the unlimited organic ligands that can be extended for additional metal nodes, 50,51 crown ether with the ability of directional coordination in cages.…”

“…We found that pure organic ligands with −CC, −P, and −S directly chelating CMCs for cage structures are indeed difficult to control, because of the nondirectional coordination − and sensitive metal–metal bonds which resulted in easy transformation or dissociation of CMCs due to slight variations in synthesis conditions. − To overcome this issue, we conjure up a new strategy that combines the merits of CMCs and traditional metal nodes in metallacages: dual nodes for metallacages are expected to alleviate the stringent requirements of curvature of CMCs as nodes in whole-cage structure and to make use of the controllable coordination direction of traditional metal nodes. Considering the unlimited organic ligands that can be extended for additional metal nodes, , we focus on luminescent CMC-based spacers whose terminal groups are functionalized by carboxylate and crown ether with the ability of directional coordination in cages.…”

Biomimetic Cu4 Cluster Encapsulated within Hollow Titanium-Oxo Nanoring for Electrochemical CO2 Reduction to Ethylene

“…Typically, polynuclear Cu clusters are synthesized using external protecting organic ligands, such as phosphines, amines, thiolates, and alkyls. − As a result, some small Cu clusters, including several Cu 4 clusters, have been obtained. , However, most of these small Cu clusters are quite different in structure from the Cu Z cluster. Mankad reported several [Cu 4 S] clusters which have N 2 O reductase activities, opening the door for these bioinspired Cu clusters to their practical application in the conversion of greenhouse gases. , In addition, the known Cu clusters usually consist of Cu I centers which are generally sensitive to oxidation, making them easily agglomeration and deactivate during the catalytic process .…”