The First Example of a Polymer‐Crystal–Organic‐Dye Composite Material: The Clathrate Phase of Syndiotactic Polystyrene with Azulene

Abstract

Annealing was carried out in air into an open joule furnace; the temperature was monitored with a K-type thermocouple. Samples were kept separated from the furnace walls by ceramic spacers. An uncoated quartz substrate was annealed at the same time. The thermal treatment did not cause any alteration in the substrate optical properties.UPS and XPS were performed in a ultrahigh vacuum analysis chamber (base pressure < 1 10 ±6 Pa) equipped with an electrostatic hemispherical analyzer. An Mg-anode source (1253.6 eV) was used for XPS, while He I (21.2 eV) and He II (40.8 eV) resonance lines were utilized for UPS. The overall energy resolution was about 1 eV in XPS and 0.1 eV in UPS. The Fermi level was identified by UPS measurement on a metallic sample. The sputtering of the films was performed by Ar ions (1.5 keV, 3.5±4.2 lA, 30 min each at 1 10 ±4 Pa). The AFM characterization was performed using a Digital Instruments Multimode Nanoscope IIIa atomic force microscope operated in tapping mode and equipped with single-crystal silicon tips. The average crystallite (grain) sizes of the samples were extracted from AFM images using software developed in our laboratory.UV-vis transmittance measurements were obtained with a JAS-CO 7850 spectrophotometer, while the optical gap values were extracted from transmittance measurements using the Tauc Polymer-based composite materials with functional organic molecules such as organic dyes have often been made by dispersing functional molecules in amorphous polymers or amorphous regions of crystalline polymers. However, such composite materials combined with functional organic molecules in the crystalline regions of polymers have not been developed hitherto, since the unit cell of most polymers has been considered to have insufficient space to store functional organic molecules. Nevertheless, the clathration of functional organic molecules within polymer crystalline regions has the advantages of preventing them from coagulation and making it possible to control their arrangement by regulating the orientation of the polymer crystalline regions. In this paper, we demonstrate the first examples of composite materials formed from organic dyes and the crystalline regions of a polymer and control of the dye-molecule orientation, both of which can be accomplished by technically simple methods. COMMUNICATIONS

Nanostructured TiO2 Films with 2 eV Optical Gap

“…Following the Tauc approach, [28] we found an optical gap (E g ) of 3.36 eV in the as-deposited samples, in agreement with the observation for amorphous TiO 2 . [9] The annealed samples…”

“…UV-vis transmittance measurements were obtained with a JAS-CO 7850 spectrophotometer, while the optical gap values were extracted from transmittance measurements using the Tauc model [28]. Polymer-based composite materials with functional organic molecules such as organic dyes have often been made by dispersing functional molecules in amorphous polymers or amorphous regions of crystalline polymers.…”

Sorption of Pollutant Traces by Nanoporous Crystalline Aerogels: Visualization by a Dye

“…Azulene is a molecule capable to form a clathrate phase with sPS by soaking d sPS films in concentrated acetone solutions containing azulene or by exposing the films to azulene vapor for several days. [9] The principle aim of this work was to make visible to the naked eye the influence of the aerogel crystalline nanopores on the sorption of pollutant traces from aqueous solutions.…”

Complexation of Syndiotactic Polystyrene with 12‐Crown‐4

“…Furthermore, it is probable that a new kind of functional materials will be developed by combining the characteristics of a host polymer lattice and a doped guest compound. So far, many organic compounds have already been incorporated into the sPS complex such as dye, [4] fluorescent, [5] photoreactive, [6] and paramagnetic molecules, [7] and so on.…”