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)4Cl2] (Cu18), 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 Cu6 octahedral kernel, whereas unoccupied orbitals owe a contribution to the distorted Cu5 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 β-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.
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