Excited State Dynamics of Geometrical Evolution of α-Substituted Dibenzoylmethanatoboron Difluoride Complex with Aggregation-Induced Emission Property.

Organic molecules with an aggregation-induced emission (AIE) property have been attracting much attention from the viewpoint of application to solid state emissive materials. For the AIE mechanism, quantum mechanical studies proposed the restriction of the intramolecular motion (RIM) model with the contribution of the conical intersection (CI) and deduced the importance of the restricted access to a conical intersection (RACI) in the potential energy surface (PES). Although these theoretical studies have contributed to the elucidation of AIE phenomena, direct detection of the reaction dynamics is indispensable to clarify the actual PES and the deactivation mechanism.

Visible-Light-Driven C-H Imidation of Arenes and Heteroarenes by a Phosphonium Ylide Organophotoredox Catalyst: Application to C-H Functionalization of Alkenes.

Phosphonium ylide catalysis through an oxidative quenching cycle has been developed for visible-light-driven C-H imidation of arenes and heteroarenes. The present protocol could be applied not only to trihalomethylative lactonization reactions involving trifluoromethyl, trichloromethyl, and tribromomethyl radicals but also to the first example of an organophotoredox-catalyzed imidative lactonization reaction involving a nitrogen-centered electrophilic radical species.

Flapping motion as a fluorescent probe for assembly process involving highly viscous liquid-like cluster intermediates during evaporative crystallization.

Fluorescence probes are widely used to assess the molecular environment based on their photo-physical properties. Specifically, flexible and aromatic photo-functional system (FLAP) is unique viscosity probe owing to the excited-state planarization of anthracene wings. We have previously applied fluorescence spectroscopy to monitor the evaporative crystallization of solvents.

Molecular Aggregation Dynamics via a Liquid-like Cluster Intermediate during Heterogeneous Evaporation as Revealed by Hyperspectral Camera Fluorescence Imaging.

A hyperspectral camera (HSC) is a camera with great potential to obtain spectral information at each pixel, together with spatial imaging. HSC fluorescence imaging enables the molecular aggregation dynamics of the evaporative crystallization process to be followed in real-time. The key intermediate liquid-like cluster state for the two-step nucleation mechanism is visualized by the fluorescence color changes of mechanochromic luminescent dibenzoylmethanatoboron difluoride derivatives.

Real-Time Fluorescence Visualization of Nanoparticle Aggregation and the Polymorph-Transition Process of a Mechanofluorochromic Difluoroboron-β-Diketone Derivative.

The use of organic nanomaterials in biomedical and optical devices has been widely studied. The key to improving the performance and stability of these devices is to control the fabrication process, which determines the phase stability and photophysical properties. In this study, fluorescence changes were observed during the reprecipitation process of mechanofluorochromic molecules of dibenzoyl(methanato)boron difluoride.

A phosphonium ylide as a visible light organophotoredox catalyst.

A phosphonium ylide-based visible light organophotoredox catalyst has been designed and successfully applied to halohydrin synthesis using trichloroacetonitrile and epoxides. An oxidative quenching cycle by the ylide catalyst was established, which was confirmed by experimental mechanistic studies.

Electronic interactions between a quaternary pyridyl-β-diketonate and anionic clay nanosheets facilitate intense photoluminescence.

Electrostatic interactions between a quaternary pyridyl-β-diketonate and anionic charged nanosheets were observed to produce a highly emissive dispersion in a rich water solution. A greater fluorescence quantum yield of approximately 50% was obtained when a luminogenic β-diketonate, 1-(4-methoxyphenyl)-3-(3-hydroxyethyl-pyridinium bromide)-1,3-propandione (prepared by the Claisen condensation reaction and subsequent quaternization), was molecularly dispersed and enclosed by a couple of atomically flat ultrathin (approximately 1.0 nm) silicate sheets of anionic layered clay.

Use of Aggregation-Induced Emission for Selective Detection of Phase Transformation during Evaporative Crystallization of Hexaphenylsilole.

Crystallization of organic molecules is quite complicated because the crystallization process is governed by weak intermolecular interactions. By exploiting aggregation-induced emission (AIE), we attempted to realize the selective detection of phase transformation during the evaporative crystallization of hexaphenylsilole (HPS), which shows different fluorescent colors in the amorphous and crystalline phases. No fluorescence emission was observed in the HPS solution immediately after dropping on the glass substrate due to the non-radiative deactivation induced by intramolecular rotational or vibrational motion, suggesting that HPS exists as a monomer in solution.

Intermolecular Dynamics of Perylene in Polymer Matrices during the Drop-Casting Process Probed by Fluorescence and Droplet Mass Changes.

This work examines the drop-casting process of a perylene-doped polymer film by monitoring the changes in fluorescence and droplet mass. The mass is then used to estimate the mean intermolecular distance r( t) changes during the casting process. At a low perylene concentration (0.

Laser-induced reprecipitation of pyrene at 77 K and its dynamics as studied by spectroscopic techniques.

Reprecipitation of pyrene (Py) in the glassy solution of methylcyclohexane and isopentane at 77 K was observed by the repetitive irradiation of nanosecond (ns) laser pulses at 355 nm. The dynamics and mechanism of this reprecipitation were investigated by means of time-resolved fluorescence and absorption spectroscopies. Although only the fluorescence of the Py monomer was observed before the ns laser irradiation, fluorescence of the excimer was observed during the initial one-shot laser irradiation.

Revealing the Origins of Mechanically Induced Fluorescence Changes in Organic Molecular Crystals.

Mechanofluorochromic molecular materials display a change in fluorescence color through mechanical stress. Complex structure-property relationships in both the crystalline and amorphous phases of these materials govern both the presence and strength of this behavior, which is usually deemed the result of a mechanically induced phase transition. However, the precise nature of the emitting species in each phase is often a matter of speculation, resulting from experimental data that are difficult to interpret, and a lack of an acceptable theoretical model capable of capturing complex environmental effects.

Dynamic Polymorph Formation during Evaporative Crystallization from Solution: The Key Role of Liquid-Like Clusters as "Crucible" at Ambient Temperature.

Understanding the polymorph phenomenon for organic crystals is essential for the development of organic solid materials. Here, the fluorescence study of the evaporative crystallization of 1,3-dipyrrol-2-yl-1,3-propanedione boron difluoride complex (1), which has three polymorphs showing different emission profiles, is reported. The droplet of 1 in 1,2-dichloroethane showed blue emission just after dropping.

Photoluminescence by Intercalation of a Fluorescent β-Diketone Dye into a Layered Silicate.

A β-diketone dye was packed into the two-dimensional nanospace of a synthetic smectite (Sumecton SA), which is a cation-exchangeable layered silicate, to induce strong emission owing to molecular packing of the dye. An emissive dye, 1-(4-methoxyphenyl)-3-(4-pyridyl)-1,3-propandione, was prepared through a Claisen condensation reaction; the dye exhibited aggregation-induced emission, which is enhanced emission owing to clustering of molecules to form aggregates in poor solvents or in the solid state. The dye was nonemissive in solution.

AIE phenomena of a cyanostilbene derivative as a probe of molecular assembly processes.

The initial processes of the crystallization of a solute molecule, 1-cyano-trans-1,2-bis-(4'-methylbiphenyl)-ethylene (CN-MBE) in binary solution (water and acetone), were investigated by means of fluorescence spectroscopy as well as scanning electron microscopy (SEM). With an increase in the volume fraction (V) of the poor solvent (water) in the solution, a drastic change in the fluorescence spectra and intensity of CN-MBE was observed. This change was attributed to aggregation induced emission (AIE).

Direct Visualization of the Two-step Nucleation Model by Fluorescence Color Changes during Evaporative Crystallization from Solution.

The two-step nucleation model for crystal nuclei formation explains several experimental and theoretical results better than the classical nucleation theory. We report here direct visualization of the two-step nucleation model for organic molecular crystallization. Evaporative crystallization from a solution of a dibenzoylmethane boron complex that displays mechanofluorochromism, a fluorescence color change induced by mechanical perturbation, was probed by fluorescence change.

Substituent-dependent backward reaction in mechanofluorochromism of dibenzoylmethanatoboron difluoride derivatives.

The thermally backward reaction involved in the mechanofluorochromism of dibenzoylmethanatoboron difluoride (BF2DBM) derivatives, accompanied by an amorphous-crystalline phase transition, was quantitatively evaluated based on kinetics and thermodynamics. The kinetics was discussed by evaluation of the effect of temperature on the time-dependent changes of the fluorescence intensity for amorphous samples obtained by mechanical grinding. The thermodynamics was discussed based on data for the amorphous-crystalline phase transition obtained by differential scanning calorimetry.

Solvent Viscosity Effect on Triplet-Triplet Pair in Triplet Fusion.

The effect of the solvent viscosity dependence of time-resolved magnetoluminescence (ML) on the delayed fluorescence of 9,10-diphenylanthracene (DPA) sensitized by platinum octaethylporphyrin has clarified the structure and dynamics of the triplet-triplet pair (TT), i.e., the transition state of triplet fusion.

Properties and evolution of emission in molecular aggregates of a perylene ammonium derivative in polymer matrices.

Size-dependent fluorescent properties of aggregates of a perylene ammonium derivative (PeryAm) were studied by steady-state and time-resolved spectroscopic methods. Quantitative analyses of aggregated states in aqueous solution indicated that the aggregation proceeded through dimer units of PeryAm. The fluorescence of the aggregate in the PVA film prepared from the aqueous solution continuously redshifted with an increase in the concentration of PeryAm in the mother liquor while keeping the absorption spectra in almost the same band shapes.

Fluorescence spectral changes of perylene in polymer matrices during the solvent evaporation process.

This work examined concentration-dependent variations in the fluorescence spectra of solutions of perylene and PMMA in toluene during the process of evaporation, using fluorescence microscopy. At low perylene concentrations, the fluorescence spectra of the resulting perylene/PMMA films exhibited a structural band originating from monomeric perylene. Increasing the concentration resulted in the appearance of new, broader bands due to the formation of two excimer species.

Fluorescence properties of pyrene derivative aggregates formed in polymer matrix depending on concentration.

We investigated the fluorescence properties of dye aggregates formed in a poly(vinylalcohol) (PVA) matrix by phase separation. Trimethyl-(2-oxo-2-pyrene-1-yl-ethyl)-ammonium bromide (PyAm) was used as a fluorescent dye molecule. The size of PyAm aggregates in the PVA thin films were increased with increasing dye concentration, which was confirmed by atomic force microscope (AFM) measurements.

Excited-state relaxation process of free-base and oxovanadium naphthalocyanine in near-infrared region.

Excited-state relaxation process of free-base and oxovanadium naphthalocyanine (H(2)Nc and VONc) in solutions and in polymer films was studied by transient absorption measurements. In polymer films only H-aggregate was observed with H(2)Nc with increasing its weight fraction, whereas VONc formed both H- and J-type aggregates. The transient absorption of singlet excited-state of H(2)Nc and VONc in toluene solution decayed with time constant of 250 +/- 30 and 12 +/- 2 ps, respectively.

Time-resolved studies of energy transfer from meso-tetrakis(N-methylpyridinium-4-yl)- porphyrin to 3,3'-diethyl-2,2'-thiatricarbocyanine iodide along deoxyribonucleic acid Chain.

The excitation energy transfer from meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) to 3,3'-diethyl-2,2'-thiatricarbocyanine iodide (DTTCI) along the deoxyribonucleic acid (DNA) double strand was investigated by the steady-state absorption and fluorescence measurements and time-resolved fluorescence measurements. The steady-state fluorescence spectra showed that the near-infrared fluorescence of DTTCI was strongly enhanced up to 86 times due to the energy transfer from the excited TMPyP molecule in DNA buffer solution. Furthermore, we elucidated the mechanism of fluorescence quenching and enhancement by the direct observation of energy transfer using the time-resolved measurements.

Photoinduced electron transfer and excitation energy transfer in directly linked zinc porphyrin/zinc phthalocyanine composite.

Photoinduced electron transfer (ET) and excitation energy transfer (ENT) reactions in monomer and slipped-cofacial dimer systems of a directly linked Zn porphyrin (Por)-Zn phthalocyanine (Pc) heterodyad, ZnPc-ZnPor, were investigated by means of the picosecond and femtosecond transient absorption spectroscopies. In the dimer dyad system of two heterodyads connected through the coordination bond between two imidazolyl-substituted ZnPor bearing ZnPc, ZnPc-ZnPor(D), the rapid ENT from the ZnPor to ZnPc in the subpicosecond time region was followed by photoinduced charge separation (CS) and charge recombination (CR) with time constants of 47 and 510 ps, respectively. On the other hand in the monomer dyad system, no clear charge-separated state was observed although the CS with a time constant of 200 ps and CR with < or =70 ps were estimated.

Carrier generation process on photoconductive polymer films as studied by magnetic field effects on the charge-transfer fluorescence and photocurrent.

We have studied the magnetic field effects (MFEs) on the charge-transfer fluorescence and transient photocurrent of a 1,2,4,5-tetracyanobenzene-doped poly(N-vinylcarbazole) film, which reflect the recombination and escape yields of the carriers, respectively. The recombination yield dependence of the external magnetic field (B) clearly shows two types of the MFEs, growth with increasing B due to the hyperfine mechanism (HFM) and a negative dip due to the level-crossing mechanism (LCM). On the other hand, the escape yield indicates complementary MFEs with a sharp decrease in yield with increasing B and then a positive dip.