[Cu18H3(S-Adm)12(PPh3)4Cl2]: fusion of Platonic and Johnson solids through a Cu(0) center and its photophysical properties

Structural elucidation of atom-precise thiolate-protected copper nanoclusters (Cu NCs) containing Cu(0) is quite challenging. Here, we report a new adamantane-thiol-protected NC, [Cu18H3(S-Adm)(12)(PPh3)(4)Cl-2] (Cu-18), which represents the first observation of a rare mononuclear Cu(0)-containing Cu10H3Cl2 core that is constructed via kernel fusion through vertex sharing of the Platonic-solid- and Johnson-solid-geometry-like kernels and hydride-bridging. The unique core is surrounded by a Cu8S12P4 metal-ligand motif shell and adopts a butterfly-like structure. In comparison to its closest structural analogue, the predominant effect of the principal Cu atom vacancy-induced structural rearrangement is evidenced. The occupied orbitals of this NC have a major d-orbital contribution to the distorted Cu-6 octahedral kernel, whereas unoccupied orbitals owe a contribution to the distorted Cu-5 square-pyramidal kernel. Thus, the charge transfer phenomenon is uniquely instigated between the two fused kernels through Cu(d) -> Cu(d) transition via the Cu(0) center. This NC exhibits violet emission due to kernel-dominated relaxation at room temperature, which is further enhanced by confining the surface protecting ligands through recognition-site-specific host-guest supramolecular adduct formation by beta-cyclodextrin. The unique electronic structure of this NC further facilitates its application toward photocurrent generation. Thus, this study offers a unique strategy for the controllable synthesis of a Cu(0)-containing Cu NC, which enables atomic-level insights into their optoelectronic properties.

Automated summary

This study reports a new thiol-protected copper nanocluster with a rare Cu(0)-containing core. The unique structure and electronic properties of this nanocluster enable it to exhibit violet emission at room temperature through charge transfer phenomena. The optical properties are further enhanced by confining the surface protecting ligands with β-cyclodextrin supramolecular adduct formation.