Facile Preparation of TICT@MOF Solids with Unprecedented PL Quantum Yields

Abstract Luminescent solids exhibit unique optical and electronic properties, and it is important to develop a simple experimental procedure to reduce the mass of weakly emissive hybrid inorganic–organic solids. The instant mixing of (1‐cyano‐2‐α‐terthiophen‐2‐yl‐vinyl)carboxylic acid (3TCC) and a metal–organic framework (MOF‐177; ZnO 4 (BTB) 2 ; BTB = 1,3,5‐benzenetribenzoate) in an organic solvent, followed by evaporation of the solvent, produces solids with distinct photoluminescence (PL) properties, turning over the PL quantum yields (PLQY) of the generated 3TCC@MOF‐177 solids by 2‐ to 40‐fold compared to the 3TCC solution is demonstrated. The new solids are characterized by various methods and optical measurements. Contrarily to the trend in the photophysical results of 3TCC solutions, the anisotropic rotational times of 3TCC@MOF‐177 solids inversely correlate with the corresponding PLQY values depending on the protic solvent used in the initial preparation step in the following order: methanol>ethanol>butanol. This behavior is attributed to the complexation of 3TCC dye with metal clusters within the pores of MOF‐177 and hydrogen bonding of the CN group in the dye with the OH group in the linkers. These factors interplay with the kinetics of dye twisting. These observations reflect the potential of new solid luminescent architectures with remarkable PLQY that can be easily manufactured.