Anion-Dependent Structure and Luminescence Diversity in Zn^II-Ln^III Heterometallic Architectures Supported by a...

To advance the structural development and fully explore the application potential, it is highly desirable but challenging to elucidate the relationship between the structures and properties of Zn^II-Ln^III heterometallic species. Herein, three types of Zn^II-Ln^III heterometallic compounds (Ln^III = Gd^III, Tb^III) formulated as [Zn₁₆Ln₄L₁₂(μ₃-O)₄(NO₃)₁₂]·8CH₃CN (ZnLn-1), [Zn₂Ln₂L₂(NO₃)₆(H₂O)₂]·3CH₃CN (ZnLn-2), and [Zn₄Ln₂L₈(OAc)₁₂]·xCH₃CN (ZnLn-3: for Ln = Gd, x = 5; for Ln = Tb, x = 4) were dictated by common inorganic anions, NO₃^- and OAc^-, with the aid of the multidentate ligand HL with propane as the central skeleton and 3-methoxysalicylamide and 3-methoxysalicylaldimine as terminal groups. ZnLn-1 features cubic cages with four {Zn₄L₃} tetrahedral subunits and four Ln³⁺ centers positioned at the eight vertices alternately when NO₃^- was introduced into the reaction system exclusively. An attempt to replace NO₃^- in ZnLn-1 with OAc^- partially led to the formation of {Zn₂Ln₂L₂} heterometallic wheels. Meanwhile, ZnLn-3 featuring double-hairpin-like {Zn₄Ln₂L₄} hemicycles that are orthogonal to each other assisted by intermolecular hydrogen bonds was constructed when NO₃^- in ZnLn-1 was completely replaced by OAc^-. Their structural integrity in solution were ascertained by both emission and ¹H NMR spectroscopy. Ascribed to the different Zn²⁺-containing antenna, ZnTb-2 possesses a relatively strong emission characteristic of Tb³⁺; ZnTb-1 has moderate Tb³⁺ luminescence, yet an absence of Tb³⁺ emission is found in ZnTb-3. Such an emission difference could be mainly attributed to the antenna effect directed by distinct structural characteristics induced by anions. The anion-dictated self-assembly strategy presented herein not only offers a facile approach to regulate the coordination mode of HL to such an extent to obtain diverse structures of Zn^II-Ln^III heterometallic species but also provides an understanding of how common inorganic anions tune coordination-driven self-assemblies as well as the subsequent luminescence properties.