Controlling the Twisted Intramolecular Charge-Transfer Character of Pyrene Derivatives Through Solvent Polarity

Intramolecular charge transfer (ICT) plays a critical role in determining the photophysical properties of organic molecules, including their luminescence efficiencies. Twisted intramolecular charge transfer (TICT) is a process in which structural change accompanies ICT. Despite significant research, the relationship between TICT and solvent polarity, and its effects on photophysical properties, have been rarely investigated. Herein, we used time-resolved spectroscopy to study TICT in pyrene derivatives that are promising blue organic light emitting diode (OLED) emitter candidates; these derivatives show strong solvent-dependent charge-transfer (CT) behavior. Slight structural changes that do not affect excited state dynamics were observed in nonpolar solvents, while polar solvents were found to affect excited state dynamics and CT characteristics. The TICT behavior of these pyrene derivatives could be modulated through structural modification. Our study provides valuable guidelines for the control of optical properties, including the luminescence efficiencies of OLED emitters that show TICT characteristics.

A Novel Dialkylamino GFP Chromophore as an Environment-Polarity Sensor Reveals the Role of Twisted Intramolecular Charge Transfer

We discovered a novel fluorophore by incorporating a dimethylamino group (–NMe2) into the conformationally locked green fluorescent protein (GFP) scaffold. It exhibited a marked solvent-polarity-dependent fluorogenic behavior and can potentially find broad applications as an environment-polarity sensor in vitro and in vivo. The ultrafast femtosecond transient absorption (fs-TA) spectroscopy in combination with quantum calculations revealed the presence of a twisted intramolecular charge transfer (TICT) state, which is formed by rotation of the –NMe2 group in the electronic excited state. In contrast to the bright fluorescent state (FS), the TICT state is dark and effectively quenches fluorescence upon formation. We employed a newly developed multivariable analysis approach to the FS lifetime in various solvents and showed that the FS → TICT reaction barrier is mainly modulated by H-bonding capability instead of viscosity of the solvent, accounting for the observed polarity dependence. These deep mechanistic insights are further corroborated by the dramatic loss of fluorogenicity for two similar GFP-derived chromophores in which the rotation of the –NMe2 group is inhibited by structural locking.