Abstract
Conceptually mimicking biomolecules' ability to construct multiple-helical aggregates with emergent properties and functions remains a long-standing challenge. Here we report an atom-precise 18-copper nanocluster (NC), Cu18H(PET)14(TPP)6(NCS)3 ( Cu18H ) which contains a pseudo D3-symmetrical triple-helical Cu15 core. Structurally, Cu18H may be also viewed as sandwich type of sulfur-bridged chiral copper cluster units [Cu6-Cu6-Cu6], endowing three-layered 3D chirality. More importantly, the chiral NCs are aggregated into an infinite double-stranded helix supported by intra-strand homonuclear C-H···H-Cdihydrogen contacts and inter-strand C-H/π and C-H/S interactions. The unique multi-layered 3D chirality and the double-helical assembly of Cu18H are evocative of DNA. Moreover, the collective behaviours of the aggregated NCs not only exhibit crystallization-induced emission enhancement (CIEE) and aggregation-induced emission enhancement (AIEE) effects in the deep-red region, but also efficiently catalyzes electron transfer (ET) reaction. This study thus presents that hierarchical assemblies of atomically defined copper NCs could be intricate as observed for important biomolecules like DNA with emergent properties arising from aggregated behaviours.
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