Polyketone-Based Anion-Exchange Membranes for Alkaline Water Electrolysis.

Anion-exchange membranes (AEMs) are involved in a wide range of applications, including fuel cells and water electrolysis. A straightforward method for the preparation of efficient AEMs consists of polymer functionalization with robust anion-exchange sites. In this work, an aliphatic polyketone was functionalized with 1-(3-aminopropyl)imidazole through the Paal-Knorr reaction, with a carbonyl (CCO %) conversion of 33%. The anion-exchange groups were generated by the imidazole quaternization by using two different types of alkyl halides, i.e., 1,4-iodobutane and 1-iodobutane, with the aim of modulating the degree of crosslinking of the derived membrane. All of the membranes were amorphous (Tg ∼ 30 °C), thermally resistant up to 130 °C, and had a minimum Young's modulus of 372 ± 30 MPa and a maximum of 86 ± 5 % for the elongation at break for the least-crosslinked system. The ionic conductivity of the AEMs was determined at 25 °C by electrochemical impedance spectroscopy (EIS), with a maximum of 9.69 mS/cm, i.e., comparable with that of 9.66 mS/cm measured using a commercially available AEM (Fumasep-PK-130). Future efforts will be directed toward increasing the robustness of these PK-based AEMs to meet all the requirements needed for their application in electrolytic cells.

Mechanochromic LLDPE Films Doped with NIR Reflective Paliogen Black.

The perylene bisimide derivative Paliogen Black (P-black) is proposed as a new chromogenic probe that shows visible (vis) and near-infrared (NIR) responses after mechanical solicitations of host linear low-density polyethylene (LLDPE) films. P-black is reported to display strong absorption in the vis spectrum and unusual reflective and cooling features in the NIR region. Uniaxial deformation of the 2.5, 5, and 10 wt% P-black/LLDPE films yields a dichroic absorption under polarized light with color variations attributed by the computational analysis to the distinct anisotropic behavior of the transition dipole moments of P-black chromophores. When LLDPE films are deformed, P-black aggregates reduce their size from ≈30-40 µm to ≈5-10 µm that, in turn, causes reflectivity losses of about 30-40% at the maximum elongation. This gives rise to warming of 5-6 °C of the locally oriented film placed in contact with a black substrate under the illumination with an IR lamp for 5 s. These features combined with the high sensitivity of the vis-NIR response toward mechanical solicitations render P-black as a new solution to detect uniaxial deformations of plastic films through both optical and thermal outputs.

Aggregation Effects on Pigment Coatings: Pigment Red 179 as a Case Study.

Here, we have studied, with a combined experimental and computational approach, the effect of the crystal environment and aggregation on the electronic properties of Pigment Red 179, which affect both its color and optical energy gap. Spectra acquired in the near-infrared and visible range of energies suggest that this molecule is indeed a "cool" dye, which can be employed as a red pigment that provides effective color coverage to different substrates without contributing to their heating during light irradiation. Spectra acquired on different polymer mixtures at different pigment concentrations (i.e., 2.5-10 wt %) suggest that absorption features depend on chromophoric arrangements promoted by the strong intermolecular π-π interactions. Calculations, performed at the time-dependent density functional theory level, allowed to both attribute the nature of the electronic transitions causing the observed spectra involved and understand the effect of the environment. Indeed, the visible spectra of the pigment is dominated by two localized transitions, with negligible charge transfer for both a dye monomer and dimer either in vacuum or acetonitrile solution. Instead, models including the crystal environment of the pigment show the presence of a high-wavelength S1 ← S0 charge transfer transition between two adjacent molecules, in quantitative agreement with the experimental absorption energy of the crystal pigment.

Fluorescent Polystyrene Films for the Detection of Volatile Organic Compounds Using the Twisted Intramolecular Charge Transfer Mechanism.

Thin films of styrene copolymers containing fluorescent molecular rotors were demonstrated to be strongly sensitive to volatile organic compounds (VOCs). Styrene copolymers of 2-[4-vinyl(1,1'-biphenyl)-4'-yl]-cyanovinyljulolidine (JCBF) were prepared with different P(STY-co-JCBF)(m) compositions (m% = 0.10-1.00) and molecular weights of about 12,000 g/mol. Methanol solutions of JCBF were not emissive due to the formation of the typical twisted intramolecular charge transfer (TICT) state at low viscosity regime, which formation was effectively hampered by adding progressive amounts of glycerol. The sensing performances of the spin-coated copolymer films (thickness of about 4 µm) demonstrated significant vapochromism when exposed to VOCs characterized by high vapour pressure and favourable interaction with the polymer matrix such as THF, CHCl3 and CH2Cl2. The vapochromic response was also reversible and reproducible after successive exposure cycles, whereas the fluorescence variation scaled linearly with VOC concentration, thus suggesting future applications as VOC optical sensors.

Vapochromic features of new luminogens based on julolidine-containing styrene copolymers.

We report on vapochromic films suitable for detecting volatile organic compounds (VOCs), based on new polystyrene copolymers containing julolidine fluorescent molecular rotors (JCAEM). Poly(styrene-co-hydroxyethylmethacrylate) copolymers functionalized with cyanovinyl-julolidine moieties of different compositions were prepared, (P(STY-co-JCAEM)(m) with m = 0.06-0.61). The sensing performance of the spin-coated copolymer films demonstrated significant vapochromism when exposed to VOCs characterized by high vapour pressure and a favourable interaction with the polymer matrix, such as Et2O and CH2Cl2. It is worth mentioning that the fluorescence decrease rate was 7 times faster than that of previously investigated julolidine-based fluorescent molecular rotors dispersed in PS films. This phenomenon was attributed to the better control of the JCAEM moiety distribution in the polymer matrix conferred by the covalent approach, combined with a minimal film thickness of 4 microns. These factors, in concert, strongly accelerate the deactivation pathways of the JCAEM units in the presence of VOCs which interact well. Overall, the present results support the use of julolidine-enriched styrene copolymers as effective chromogenic materials suitable for the fast detection of VOCs.

Tuning of dye optical properties by environmental effects: a QM/MM and experimental study.

The present work is aimed at a deeper investigation of two recently synthesized heteroaromatic fluorophores by means of a computational multilayer approach, integrating quantum mechanics (QM) and molecular mechanics (MM). In particular, dispersion of the title dyes in a polymer matrix is studied in connection with potential applications as photoactive species in luminescent solar concentrators (LSCs). Molecular dynamics simulations, based on accurate QM-derived force fields, reveal increased stiffness of these organic dyes when going from CHCl3 solution to the polymer matrix. QM/MM computations of UV spectra for snapshots extracted from MD simulations show that this different flexibility permits explaining the different spectral shapes obtained experimentally for the two different environments. Moreover, the general spectroscopic trends are reproduced well by static computations employing a polarizable continuum description of environmental effects.

Vapochromic Behaviour of Polycarbonate Films Doped with a Luminescent Molecular Rotor.

We report on vapochromic films suitable for detecting volatile organic compounds (VOCs), based on polycarbonate (PC) doped with 4-(triphenylamino)phthalonitrile (TPAP), a fluorescent molecular rotor sensitive to solvent polarity and viscosity. PC films of variable thickness (from 20 up to 80 µm) and containing small amounts of TPAP (0.05 wt.%) were prepared and exposed to a saturated atmosphere of different VOCs. TPAP/PC films showed a gradual decrease and red-shift of the emission during the exposure to solvents with high polarity index and favourable interaction with the polymer matrix such as THF, CHCl3, and acetonitrile. In the case of the most interacting solvents (THF and CHCl3), TPAP/PC films also showed a fluorescence increase at longer exposure times, as a consequence of an irreversible, solvent-induced crystallization process of the polymeric matrix. The vapochromism of TPAP/PC films is rationalized on the basis of alterations of the rotor intramolecular motion upon solvent uptake by PC and polarity effects of the microenvironment. Interestingly, the fluorescence response of the TPAP/PC films shows a non-trivial, tuneable dependence on film thickness during the second solvent-exposure stage. The latter effect is attributed to a variable extent of the crystallization process occurring in the PC films. This observation promptly suggests, in turn, an effective procedure to modulate the spectroscopic response in such functionalized polymeric materials through the precise control of the film thickness.

Toward the design of alkynylimidazole fluorophores: computational and experimental characterization of spectroscopic features in solution and in poly(methyl methacrylate).

The possibilities offered by organic fluorophores in the preparation of advanced plastic materials have been increased by designing novel alkynylimidazole dyes, featuring different push and pull groups. This new family of fluorescent dyes was synthesized by means of a one-pot sequential bromination-alkynylation of the heteroaromatic core, and their optical properties were investigated in tetrahydrofuran and in poly(methyl methacrylate). An efficient in silico pre-screening scheme was devised as consisting of a step-by-step procedure employing computational methodologies by simulation of electronic spectra within simple vertical energy and more sophisticated vibronic approaches. Such an approach was also extended to efficiently simulate one-photon absorption and emission spectra of the dyes in the polymer environment for their potential application in luminescent solar concentrators. Besides the specific applications of this novel material, the integration of computational and experimental techniques reported here provides an efficient protocol that can be applied to make a selection among similar dye candidates, which constitute the essential responsive part of those fluorescent plastic materials.

Synthesis and Optical Properties of Imidazole-Based Fluorophores having High Quantum Yields.

A series of 1,4-phenylene-spaced bis-imidazoles with fluorescence quantum yields up to 0.90 and large Stokes shifts have been designed and synthesized using recently developed regioselective direct CH arylation protocols. All the fluorophores show a bright blue-green emission that is well retained in the solid state. DFT calculations attributed their excellent luminescence properties to the significant planarization of the molecules in the equilibrium structures of their excited electronic states.

Light-Responsive Polystyrene Films Doped with Tailored Heteroaromatic-Based Fluorophores.

We describe a simple but effective strategy for imparting light-responsive peculiarity to polystyrene films. A pH-sensitive fluorescent dye having the electron-poor pyridine nucleus as a key structural feature was synthesized and dispersed at low loadings (0.2-0.5 wt %) in a PS matrix. Once light irradiation in the near-UV range was sent to PS/dye films, PS photooxidation likely occurred at the film surface with the formation of carboxylic compounds. These species locally promoted dye protonation, thus, yielding a clear change of the film emission from blue to green. This study opens the door to a wide range of light-responsive materials from easily accessible polymers, enabling the use of UV light as an effective trigger for smart materials and devices.