Solvent-Directed Self-Assembly of Chiral Metal–Organic Cages and Coordination Polymers from Identical Components and Their Circularly Polarized Luminescence

Abstract This work reports the solvent-directed synthesis, structures, and chiroptical properties of enantiomeric Zn(II) metal–organic cages (MOCs) and coordination polymers (CPs) assembled from identical subcomponents under the same conditions. Varying the DMF/MeOH ratio selectively produces either a discrete cubic cage (1-R/S) or a chain polymer (2-R/S). Both materials exhibit blue emission, with the MOCs demonstrating higher solid-state quantum yields. MOCs 1-R/S in poly(methyl methacrylate) films exhibit clear circularly polarized luminescence (CPL) (|glum| ≈ 4.0 × 10–4), whereas CPs 2-R/S display very weak CPL signals (|glum| ≈ 1.0 × 10–5). This work highlights that the supramolecular structure determines the CPL performance of excited-state chirality.