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

Abstract Cu clusters are generally unstable and their cluster nuclei are difficult to be controlled. Even minor adjustments in the synthesis of Cu clusters can easily lead to great changes in their cluster nuclei. In this work, we have successfully utilized triple collaborative ligands to obtain a pair of infinitely extended Cu 12 cluster‐based chains ( Cu 12 ‐1 and Cu 12 ‐2 ). They have identical Cu 12 metal core structures but slightly different coordinated ligands. Both Cu 12 ‐1 and Cu 12 ‐2 show excellent thermal and ambient stability. However, they exhibit diverse room‐temperature photoluminescence phenomena. Crystalline Cu 12 ‐2 displays red‐shifted photoluminescence (637 nm) compared with Cu 12 ‐1 (624 nm) due to the relatively smaller LUMO‐HOMO gap caused by the substituent effect of electro‐withdrawing F atoms. Meanwhile, the substituent effect has influences on electronic structures and electrostatic potentials, thus leading to differences in photoluminescence intensity, PLQY, and lifetime. Crystalline Cu 12 ‐1 displays more intense room‐temperature photoluminescence, higher PLQY and longer lifetime. This work provides a valuable approach for how to prepare highly stable Cu clusters and precisely control their structures to regulate their properties.