Das Anish Kumar, Biswas Sourav, Wani Vaibhav S, Nair Akhil S, Pathak Biswarup, Mandal Sukhendu
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram Kerala 69551 India
Department of Chemistry, Indian Institute of Technology Indore Madhya Pradesh 453552 India.
Chem Sci. 2022 Jun 2;13(25):7616-7625. doi: 10.1039/d2sc02544b. eCollection 2022 Jun 29.
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, [CuH(S-Adm)(PPh)Cl] (Cu), which represents the first observation of a rare mononuclear Cu(0)-containing CuHCl core that is constructed 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 CuSP 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 octahedral kernel, whereas unoccupied orbitals owe a contribution to the distorted Cu square-pyramidal kernel. Thus, the charge transfer phenomenon is uniquely instigated between the two fused kernels through Cu(d) → Cu(d) transition 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.
对含有零价铜（Cu(0)）的原子精确硫醇保护铜纳米团簇（Cu NCs）进行结构解析极具挑战性。在此，我们报道了一种新型金刚烷硫醇保护的纳米团簇[CuH(S-Adm)(PPh)Cl]（Cu），这是首次观察到一种罕见的含单核Cu(0)的CuHCl核，它是通过类似柏拉图立体和约翰逊立体几何形状的核的顶点共享以及氢化物桥连构建而成的核融合结构。独特的核被一个CuSP金属 - 配体基序壳所包围，并呈现出蝴蝶状结构。与其最接近的结构类似物相比，可以证明主要铜原子空位诱导的结构重排的主要影响。该纳米团簇的占据轨道对扭曲的铜八面体核有主要的d轨道贡献，而未占据轨道则对扭曲的铜四方锥核有贡献。因此，通过Cu(d)→Cu(d)跃迁在两个融合核之间独特地引发了电荷转移现象，该跃迁发生在Cu(0)中心。由于在室温下核主导的弛豫，该纳米团簇呈现出紫色发射，通过β - 环糊精形成识别位点特异性主客体超分子加合物来限制表面保护配体，这种发射会进一步增强。该纳米团簇独特的电子结构进一步促进了其在光电流产生方面的应用。因此，本研究为可控合成含Cu(0)的铜纳米团簇提供了一种独特策略，能够在原子水平上深入了解其光电性质。
