RESUMO
Using bis(imino)acenaphthene (BIAN) zinc(II) and palladium(II) complexes with tetraphenylethene (TPE) units as bulky aryl groups, Zn-2 and Pd-2 have been designed and developed, and their photophysical properties in solution and in the solid state have been investigated. Both in solution and in the solid state Zn-2 and Pd-2 show two photoabsorption bands in the ranges of 300 nm to 350 nm and 450 nm to 600 nm, which are assigned to the π-π* transition originating from both the TPE units and naphthalene units and the intraligand charge transfer (ILCT) between the TPE units and the BIAN unit, respectively. Density functional theory (DFT) calculations demonstrated that for Zn-2 the highest occupied molecular orbitals (HOMO) are localized on the TPE units, while the lowest unoccupied molecular orbitals (LUMO) are localized on the BIAN unit, leading to the appearance of a photoabsorption band on the ILCT. The emission from Zn-2 was quenched in solution, but appeared as phosphorescence at around 600 nm by photoexcitation at the ILCT band in the solid state as well as in the aggregated state, which was formed by the addition of n-hexane as a poor solvent to the dichloromethane (DCM) solution. The aggregate formation of Zn-2 in the DCM/n-hexane (10 wt%/90 wt%) solution was confirmed by the Tyndall scattering and scanning electron microscopy (SEM) measurements, demonstrating the aggregation-induced emission (AIE) characteristics of Zn-2. On the other hand, Pd-2 was non-emissive in the solid state and in the aggregated state as well as in solution. Moreover, the DCM-inclusion complexes of Zn-2 and Pd-2 were obtained and their photophysical properties were investigated. It was found that the photoluminescence quantum yield (ΦPL-solid) values of Zn-2 and Zn-2-DCM in the solid state are less than 1%. Single-crystal X-ray structural analysis of Zn-2-DCM revealed the absence of intermolecular π-π interactions. Consequently, it was suggested that the low ΦPL-solid value of Zn-2 is mainly due to the radiationless relaxation of the excitons by dynamic rotation of the phenyl groups of the TPE units, even in the solid state and in the aggregation state.
RESUMO
Anthracene-(aminomethyl)phenylboronic acid pinacol ester (AminoMePhenylBPin) OF-2 acts as a PET (photo-induced electron transfer)-type fluorescent sensor for determination of a trace amount of water: the addition of water to organic solvents containing OF-2 causes a drastic and linear enhancement of fluorescence emission as a function of water content, which is attributed to the suppression of PET. Indeed, detection limits (DLs) for OF-2 were as low as 0.01-0.008 wt% of water in solvents, that is, the PET method makes it possible to visualize, detect, and determine a trace amount of water. Thus, in this work, in order to develop fluorescent polymeric materials for visualization and detection of water, we have achieved the preparation of various types of polymer films (polystyrene (PS), poly(4-vinylphenol) (PVP), polyvinyl alcohol (PVA), and polyethylene glycol (PEG)) which were doped with OF-2, and investigated the optical sensing properties of the OF-2-doped polymer films for water. As-prepared OF-2-doped polymer films initially exhibited green excimer emission in the PET active state, but blue monomer emission in the PET inactive state upon exposure to moisture or by water droplet. Moreover, it was found that the OF-2-doped polymer films show the reversible fluorescence properties in the dry-wet process. Herein we propose that polymer films doped with PET-type fluorescent sensors for water based on a fluorescence enhancement (turn-on) system are one of the most promising and convenient functional materials for visualizing moisture and water droplets.