With a reprecipitation method, we prepared fluorescent organic nanoparticles of 1,4-di[(E)-2-phenyl-1-propenyl]benzene (PPB) that feature weak emission in solution but exhibit blue-shifted absorption and strong emission as aggregates. Picosecond fluorescent transients of these PPB nanoparticles showed biexponential decay, described with a consecutive kinetic model involving two emissive states. X-ray diffraction patterns of PPB nanocrystals indicate long-range packing structures of two types, one the same as in a single crystal and the other not yet determined. PPB molecules in a crystal show an arrangement of a herringbone type with three benzene rings in a PPB unit being nearly planar and two methyl groups of the unit pointing along the same direction, in contrast to the twisted structure of an isolated PPB molecule. Fluorescence transients of PPB on a femtosecond scale indicate an efficient channel for isomerization that is activated for free PPB in solution but inhibited in PPB forming nanoparticles, demonstrating the significance of molecular geometry and twisting motions that affect the relaxation dynamics in the excited state. The versatile techniques combined in this work provide strong evidence to improve our understanding of optical properties in organic nanoparticles dependent on size.
Following to the recent development of the organic-templated growth of materials, new types of photonic hybrid composite materials have emerged whose structure and function are organized hierarchically. Ordered, periodic mesoscopic materials allow the construction of composites with many types of guest, such as organic molecules or polymers. These host-guest materials combine the high stability of the inorganic host system, a new structure-forming mechanism due to the confinement of guests in well-defined
Ferroelectric phase transformation characteristics of ceramic BaTiO3 have been studied by combined thermo-Raman and dielectric measurements. The temperature dependence of Raman bands at 311 and 721 cm−1 shows that tetragonal to cubic (T–C) phase transformation occurs over a range of temperature. The increase in the bandwidths of these bands indicates that this transformation is an order-disorder transformation. The differential thermo-Raman intensity thermograms show a dip at a temperature corresponding to the maximum rate of phase transformation and this temperature can be defined as phase transformation temperature Tp. The ferroelectric transformation temperature Tm corresponding to the peak in the ε(T) obtained from the temperature dependence of dielectric constant is found to coincide with Tp. This indicates that maximum in dielectric constant occurs at the maximum rate of T–C phase transformation. Both Tp and Tm exhibit thermal hysteresis. The Curie temperature TC obtained from the intersection of tangential of inverse dielectric constant to the temperature axis and is found to be less than Tm and Tp in agreement with O. G. Vendik and S. P. Zubko [J. Appl. Phys. 88, 5343 (2000)] calculations. Thermo-Raman spectroscopy coupled with dielectric constant measurement is shown to be an effective technique to investigate the phase transformation in ferroelectric materials.
We prepared the fluorescent nanobelts of cyano-substituted 1,4distyrylbenzene derivative (CNDSB) with the reprecipitation method. CNDSB is nonemissive in solution but with strong aggregation-induced emission (AIE) in belt-like structure. The molecular structure predicted by quantum chemical calculations indicates a twisted conformation of CNDSB monomer, while the solid-state X-ray structure of the CNDSB crystal features herringbone-type arrangement and three benzene rings arrange in nearly planar conformation. Femto-and picosecond time-resolved fluorescence spectroscopy are implemented to study the photophysics and the origin of the AIE effect in CNDSB nanobelts. The fluorescence quenching of CNDSB in THF solution arises from the efficient nonradiative isomerization channel. In this study, the fluorescence decay of CNDSB embedded in poly(methyl methacrylate) matrix is slowed down due to the restriction of intramolecular motions in the solid matrix. In nanobelt structure, the fluorescence lifetime further increases due to the intermolecular interaction between H-type aggregates. Both the steady-state and time-resolved studies suggests that there are at least two different packing structures might exist in nanobelts, and the relative composition of these two different structures gradually changes in different sizes of nanobelts.
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