Excited-State Rotational Dynamics of Amine-Functionalized Terephthalic Acid Derivatives as Linker Models for Metal–Organic Frameworks

Understanding how structural modifications affect the photophysics of organic linkers is crucial for their integration into metal–organic frameworks (MOFs) for light-driven applications. This study explores the impact of varying the amine functional group position on two terephthalic acid derivatives─linker 1 and linker 2─by investigating their photophysics through a combination of steady-state and ultrafast laser spectroscopy and time-dependent density functional theory (TD-DFT) calculations. With tetrahydrofuran as the solvent, time-correlated single-photon counting revealed a 2-fold increase in the S₁ excited-state lifetime of the molecule with the amine group at the meta position compared with that of the molecule with the amine group at the ortho position. This phenomenon can be attributed to restricted intramolecular twisting for the molecule with the amine group in the meta position. In this regime, an interplay of high-energy steric and conjugation barriers was revealed for the molecule with the amine group at the meta position by TD-DFT calculations. Moreover, femtosecond/nanosecond transient absorption spectroscopy revealed a reversible excited-state conformational change for the ortho isomer via intramolecular rotation that occurred within ∼110 ps, unlocking a triplet state manifold. This study underscores the importance of modifying organic emitters, either as free linkers or within MOFs, to increase their performance in sensing and light-emitting applications.