White Light Emission from Zn(II) and DMSO-Induced Copper Nanocluster Assembly

An assembly of metal nanoclusters driven by appropriate surface ligands and solvent environment may engender entirely new photoluminescence (PL). Herein, we first synthesize histidine (His) stabilized copper nanoparticles (CuNPs) and, subsequently, copper nanoclusters (CuNCs) from it using 3-mercaptopropionic acid (MPA) as an etchant. The CuNCs originally emit bluish-green (λ_em=470 nm) PL with a low quantum yield (QY∼1.8 %). However, it transformed into a dual-emissive nanocluster assembly (Zn-CuNCs) in the presence of Zn(II) salt, having a distinct blue emission band (λ_em=420 nm) and a red emission band (λ_em=615 nm) with eight times QY (∼9.1 %) enhancement. The temperature-dependent emission spectra of Zn-CuNCs depicted that the blue emission band persists for all the temperature ranges (0-80 °C) while the red emission band vanishes at high temperatures (70-80 °C). Thus, the blue emission may originate from the locally excited state (LES) emission of the nanoclusters, while the red emission originates from through-space interaction (TSI) and Cu(I)…Cu(I) interaction within the assembly. Adding dimethyl sulfoxide (DMSO) further modifies the emission intensities; the red band was amplified four times, while the blue band was diminished by 2.5 times. The transmission electron microscopy (TEM) images unveiled that the Zn-CuNCs are a large assembly of tiny nanoclusters, which become more compact in DMSO. The blue emission possesses steady-state fluorescence anisotropy, while the red emission shows no anisotropy. Further, near-perfect white light emission(WLE) was rendered with CIE coordinates of (0.33, 0.32) by combining the dual emission of the Zn-CuNCs with the original green emission of the CuNCs.