Quantitative Thermal Synthesis of Cu(I) Coordination Polymers That Exhibit Thermally Activated Delayed Fluorescence

As a new environmentally friendly route for synthesizing thermally activated delayed-fluorescence (TADF) Cu(I) complexes, we successfully and quantitatively synthesized strongly emissive Cu(I) coordination polymers [Cu₂I₂(PR₃)₂(n,n'-bpy)]_∞ (CuIR-, R = Ph, Tol; n = 3, 4; bpy = bipyridine) via the quick thermal reaction of three starting materials (CuI, PR₃, and bpy organic ligands) for 1 h in the absence of a solvent. Powder X-ray diffraction and thermogravimetric analyses revealed that melting of the organic ligands significantly promoted the coordination polymerization reaction, and the stoichiometry of three starting materials was crucial to quantitatively affording CuIR-. Notably, the photophysical properties of CuIR- obtained by the thermal reaction were almost the same (emission wavelength, quantum yield, and lifetime) as that obtained by generally used solution reactions, probably because CuIR- was thermally stable enough to prevent the thermal damage and to improve the crystallinity in the heating process. The emission origin of CuIR- was assignable to TADF at 298 K and phosphorescence at 77 K originating from the metal-to-ligand charge-transfer excited state effectively mixed with the halide-to-ligand charge transfer ((M+X)LCT) state. Thus, the thermal reaction in the melted ligand could be a promising environmentally friendly method for producing TADF Cu(I) luminophores.