Supramolecularly Dimeric Assemble of Planar Cu13 Clusters Controlled by the Length of Spacers of Diphosphine

The controlled formation of dimeric clusters is challenging. Three copper(I) clusters, labeled as {Cu13[o-Ph(C≡C)2]6(L)4}(ClO4), were synthesized by using three different ligands, including 1,4-bis(diphenylphosphino)butane (dppb), 1,5-bis(diphenylphosphino)pentane (dpppe), and bis(diphenylphosphino)hexane (dpph). By increasing the flexibility of alkyl spacers in the diphosphine ligands, the relative positions of the phenyl rings could be optimized to achieve efficient packing with maximized intercluster interactions. In the crystal structures, cluster 1 with dppb ligands did not display interlocked structures. In contrast, cluster 2 with dpppe ligands formed supramolecularly interlocked polymers through weak π–π interactions and C–H···π interactions, while cluster 3 employing dpph ligands formed supramolecularly interlocked dimers with strong π–π interactions and C–H···π interactions. The supramolecular dimer of 3 was also evidenced by analyses through electrospray ionization mass spectrometry and transmission electron microscopy. Density functional theory calculation was used to understand the electronic structure and transitions. Supramolecularly interlocked polymers/dimers with rigid structures exhibited higher quantum efficiency. The solution of these clusters demonstrated remarkable aggregation-induced emission enhancements. This study presents unique examples of planar luminescent copper clusters, featuring the first serial dialkynyl-protected cluster. It underlines the importance of ligand flexibility in creating supramolecular cluster dimers.