[Cu18H3(S-Adm)12(PPh3)4Cl2]: fusion of Platonic and Johnson solids through a Cu(0) center and its photophysical properties. Issue 25 (15th June 2022)

• Record Type: Journal Article
• Authors: Das, Anish Kumar; Biswas, Sourav; Wani, Vaibhav S.; Nair, Akhil S.; Pathak, Biswarup; Mandal, Sukhendu
• Is Part Of: Chemical science. Volume 13:Issue 25(2022)
• Page Start: 7616
• Page End: 7625
• Publication Date: 2022-06-15
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc02544b
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : An example of a butterfly-like [Cu18 H3 (S-Adm)12 (PPh3 )4 Cl2 ] cluster with vertex-sharing kernels through a Cu(0) center. Combined experimental and theoretical results correlate its photophysical properties with its unique structural architecture. Abstract : 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, [Cu18 H3 (S-Adm)12 (PPh3 )4 Cl2 ] (Cu18 ), which represents the first observation of a rare mononuclear Cu(0)-containing Cu10 H3 Cl2 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 Cu8 S12 P4 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.