Ultrahigh Aggregation Induced Emission Efficiency in Multitwist-Based Luminogens under High Pressure.

Increasing aggregation induced emission (AIE) efficiency is of fundamental interest as it directly reflects performance of multitwist-based luminogens in bioimaging and in the photoelectric device field. However, an effective and convenient methodology to increase AIE efficiency significantly remains a challenge. Here, we present a general strategy to increase AIE efficiency of multitwist-based luminogens by pressure, resulting in a 120.1-fold enhancement of the AIE intensity of tris[4-(diethylamino)phenyl]amine (TDAPA) under high pressure compared to that of the traditional method. AIE efficiency of TDAPA increases from 0.5% to 46.1% during compression. Experimental and theoretical investigations reveal that the AIE efficiency enhancement originates from intramolecular vibration and the twisted intramolecular charge transfer are suppressed under high pressure. High AIE efficiency under high pressure provides an important inspiration for improving performance of multitwist-based luminogens in the lighting and biomedical fields.

Enhancing fluorescence of benzimidazole derivative via solvent-regulated ESIPT and TICT process: A TDDFT study.

In this work, we use density functional theory and time dependent density functional theory to explore the ESIPT and TICT process of 6-(1H-Benzoimidazol-2-yl)-2,3-dimethoxy-phenol (BIDOP) in cyclohexane (CHX) and tetrahydrofuran (THF) solvent, respectively. It reveals that ESIPT process of BIDOP can occur in both CHX and THF solvent at the first excited state with similar reaction barrier. Remarkably, compared to barrierless from keto (K*) to TICT state of BIDOP in THF solvent, the reaction barrier between K* and TICT state is up to 20.28 kcal/mol for in CHX that TICT process is inhibited in CHX solvent. The absence of nonradiative decay TICT state of BIDOP in CHX solvent induces higher fluorescence in CHX compared to in THF solvent. These findings indicate that CHX solvent can effectively enhance fluorescence of BIDOP. Our study highlights a convenient approach for enhancing fluorescence and is significant for photophysics and photobiology field.

Revised the excited-state intramolecular proton transfer direction of the BTHMB molecule: A theoretical study.

The spectroscopic properties of 3-(benzo[d]-thiazol-2-yl)-2-hydroxy-5-methoxy benzaldehyde molecule were investigated [J. Phys. Chem. A 2019, 123, 10246-10253]. The result shows that the excited-state intramolecular proton transfer (ESIPT) was driven toward the N center over the O center. In this research, the density functional theory and time-dependent density functional theory method were used to calculate molecule structures. Through our calculations, the ESIPT process toward N atom is proved to be feasible. Moreover, the emission peak we obtained of ESIPT process from the OH proton to aldehyde O atom is located at 564 nm, which is attributed to 500 nm in previous research. From the potential energy curves, the 0.35 kcal/mol energy barrier indicates the ESIPT process could occur when excited to S1 state from the OH proton to aldehyde O atom. In addition, the frontier molecular orbitals analysis and IR spectrum were also calculated. Finally, we revise the direction of BTHMB molecule, the two directions of ESIPT are both feasible when excited to S1 state.

Revised excited-state intramolecular proton transfer of the 3-Aminophthalimide molecule: A TDDFT study.

The spectroscopic properties of 3-Aminophthalimide (3AP) molecule were investigated [Chem. Phys. 2002, 283, 249, New J. Chem. 2018, 42, 1181]. The result was that the 3AP molecule was exhibiting excited-state intramolecular proton transfer (ESIPT). In the research, we revised previous result using time-dependent density functional theory (TDDFT) method. The fluorescence spectrum shows that the only fluorescence peak is from initial enol form, which is different from the traditional case of ESIPT. The red shift of characteristic peaks in infrared vibration spectra is not induced by ESIPT process. The change in the vibration mode of the amino group causes the red shift of characteristic peak in the infrared spectrum. Energy curves indicate that the barrier (19.71 kcal/mol) is anomalously high in the first excited state. In addition, there are not stable points to lead the ESIPT to form a keto isomer. Together, these results demonstrate that there is not an ESIPT process happening of 3AP molecule.

The role played by solvent polarity in regulating the competitive mechanism between ESIPT and TICT of coumarin (E-8-((4-dimethylamino-phenylimino)-methyl)-7-hydroxy-4-methyl-2H-chromen-2-one).

Excited-state intramolecular proton transfer (ESIPT) and twist intramolecular charge transfer (TICT) are the two most fundamental dynamic processes, ubiquitous in biological and chemical reactions. The excited-state properties of (E-8-((4-dimethylamino-phenylimino)-methyl)-7-hydroxy-4-methyl-2H-chromen-2-one (CDPA) in various solvents with different polarities were investigated by using steady-state and femtosecond transient absorption spectroscopy combined with DFT/TDDFT calculations. The results demonstrated that CDPA exhibited low fluorescence in polar acetonitrile (ACN) due to ESIPT but high fluorescence in nonpolar n-Hexane was attributed to intramolecular rotation blocking ESIPT. TDDFT calculations confirmed that the dramatic phenyl group torsional of CDPA in Hexane, whereas a near planar conformation in ACN solvent. The ESIPT barrier decreases regularly with the increase of solvent polarity from n-Hexane, tetrahydrofuran to ACN solvent. These results demonstrated that the ESIPT and TICT processes of CDPA are competitive mechanisms. Our work revealed the effect solvent polarity on the emission behavior and excited-state deactivation mechanism of CDPA, which could help to design and develop new polarity probe in the microenvironments.

Ultrafast carrier dynamics in all-inorganic CsPbBr3 perovskite across the pressure-induced phase transition.

The excited-state carrier dynamics of lead halide perovskites play a critical role in their photoelectric properties, and are greatly affected by lattice structural changes. In this work, the carrier dynamics of all-inorganic CsPbBr3 peroveskite, as a function of pressure, are investigated using in situ high-pressure femtosecond transient absorption spectroscopic experiments. Compression is found to drive crystal structural evolution, thereby markedly changing the behavior of charge carriers in CsPbBr3. Before the phase transition, simultaneous prolonging of the carrier relaxation and Auger recombination is achieved alongside a narrowing in the bandgap. The results favor improved efficiency and photovoltaic performance.

Solvent viscosity induces twisted intramolecular charge transfer state lifetime tunable of Thioflavin-T.

Excited-state deactivation dynamics of Thioflavin-T (ThT) in gradual viscosity solvents were investigated. Femtosecond transient absorption spectra and dynamic decay curves both present significant distinction of ThT in different volume ratios binary mixtures solvents. Dynamics fitting lifetime of twisted intramolecular charge transfer (TICT) state is strongly dependent on solvents viscosity. Compared to rotation corresponding time of ThT in low viscosity solvent (0.6 cp) experimentally coincident well with Stokes-Einstein-Debye (SED) equation, the relation between rotation corresponding time and relatively high viscosity (5.9 cp to 1091.2 cp) is more consistent with fractional SED equation. Combined with optimized geometric structures of ThT by density functional theory and time-dependent density functional theory, further understand TICT state lifetime increases with increasing solvents viscosity. Our work provides a comprehensive understanding of fluorescence molecular rotor (FMR) deactivation process in different viscosity solvents and is helpful to design new FMR.