Hierarchical Self-Assembly of Luminescent Tartrate-Bridged Chiral Binuclear Tb(III) Complexes in Ethanol

A new family of supramolecular metalloamphiphiles carrying two metal centers is developed. They are formed by bridging two coordinatively unsaturated lipophilic Tb³⁺ complexes (TbL⁺) with chiral dicarboxylate anions. The formation of bridging coordination bonds is confirmed using UV spectroscopy, induced circular dichroism (ICD), increased luminescence intensity of TbL⁺, and electrospray ionization mass spectrometry (ESIMS) analysis. These supramolecular metalloamphiphiles hierarchically self-assemble in ethanol to give luminescent nanospheres, as observed using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The two hydroxyl groups introduced in the bridging ligands of [TbL]₂(d-/l-tartrate) significantly promote self-assembly by increasing coherent forces via intermolecular hydrogen bonding. The observed self-assembly in ethanol also merits mention because such polar alcoholic media have been unfavorable for conventional molecular self-assemblies. The present approach offers a new molecular design strategy for composable metalloamphiphiles.