Microporous Polymelamine Framework Functionalized with Re(I) Tricarbonyl Complexes for CO2 Absorption and Reduction.

A mixture of polymeric complexes based on the reaction between Re(CO)5Cl and the porous polymeric network coming from the coupling of melamine and benzene-1,3,5-tricarboxaldehyde was obtained and characterized by FTIR, NMR, SEM, XPS, ICP, XRD, and cyclic voltammetry (CV). The formed rhenium-based porous hybrid material reveals a noticeable capability of CO2 absorption. The gas absorption amount measured at 295 K was close to 44 cm3/g at 1 atm. An interesting catalytic activity for CO2 reduction reaction (CO2RR) is observed, resulting in a turn over-number (TON) close to 6.3 under 80 min of test at -1.8 V vs. Ag/AgCl in a TBAPF6 0.1 M ACN solution. A possible use as filler in membranes or columns can be envisaged.

Impact of the Electron Acceptor Nature on the Durability and Nanomorphological Stability of Bulk Heterojunction Active Layers for Organic Solar Cells.

A systematic study is conducted to compare the performances and stability of active layers employing a high performance electron donor (PBDB-T) combined with state-of-the-art fullerene (PC71 BM), nonfullerene (ITIC), and polymer (N2200) electron acceptors. The impact of the chemical nature of the acceptor on the durability of organic solar cells (OSCs) is elucidated by monitoring their photovoltaic performances under light exposure or dark conditions in the presence of oxygen. PC71 BM molecules exhibit a higher resistance toward oxidation compared to nonfullerene acceptors. Unencapsulated PBDB-T:PC71 BM OSCs display relatively stable performances at room temperature when stored in air for 3 months. However, when exposed to temperatures above 80 °C, their active materials demix causing notable reductions in the short-circuit densities. Such detrimental demixing can also be seen for PBDB-T:ITIC active layers above 120 °C. Although N2200 chains irreversibly degrade when exposed to air, thermally induced demixing does not occur in PBDB-T:N2200 active layers annealed up to 200 °C. In summary, fullerene OSCs may be the best currently available choice for unencapsulated room temperature applications but if oxidation of the polymer acceptors can be avoided, all polymer active layers should enable the fabrication of highly durable OSCs with lifetimes matching the requirements for OSC commercialization.

Rod-Coil Block Copolymer: Fullerene Blend Water-Processable Nanoparticles: How Molecular Structure Addresses Morphology and Efficiency in NP-OPVs.

The use of water-processable nanoparticles (WPNPs) is an emerging strategy for the processing of organic semiconducting materials into aqueous medium, dramatically reducing the use of chlorinated solvents and enabling the control of the nanomorphology in OPV active layers. We studied amphiphilic rod-coil block copolymers (BCPs) with a different chemical structure and length of the hydrophilic coil blocks. Using the BCPs blended with a fullerene acceptor material, we fabricated NP-OPV devices with a sustainable approach. The goal of this work is to clarify how the morphology of the nanodomains of the two active materials is addressed by the hydrophilic coil molecular structures, and in turn how the design of the materials affects the device performances. Exploiting a peculiar application of TEM, EFTEM microscopy on WPNPs, with the contribution of AFM and spectroscopic techniques, we correlate the coil structure with the device performances, demonstrating the pivotal influence of the chemical design over material properties. BCP5, bearing a coil block of five repeating units of 4-vinilpyridine (4VP), leads to working devices with efficiency comparable to the solution-processed ones for the multiple PCBM-rich cores morphology displayed by the blend WPNPs. Otherwise, BCP2 and BCP15, with 2 and 15 repeating units of 4VP, respectively, show a single large PCBM-rich core; the insertion of styrene units into the coil block of BCP100 is detrimental for the device efficiency, even if it produces an intermixed structure.

Hydrogels Based on Imino-Chitosan Amphiphiles as a Matrix for Drug Delivery Systems.

This paper reports new formulations based on chitosan, citral, and diclofenac sodium salt (DCF). The central idea was to encapsulate an anionic drug into a polycationic hydrogel matrix in order to increase the intermolecular forces between them and thus to ensure slower drug release, while citral was used as a penetration enhancer to assure efficient delivery of the drug. Hydrogels without drug were also synthesized and used as a reference. The structure, morphology, and supramolecular architecture of the drug delivery systems were evaluated by FTIR spectroscopy, scanning electron microscopy, polarized optical microscopy, and wide-angle X-ray diffraction. The drug release kinetics was monitored in vitro by UV-VIS spectroscopy, in physiological conditions, while the enzymatic and hydrolytic degradability of the hydrogels were evaluated in the presence of lysozyme and phosphate buffer saline (PBS), at 37 °C. All of the data revealed that the anionic DCF was strongly anchored into the polycationic matrix and the drug was slowly released over 7 days. Moreover, the release rate can be controlled by simple variation of the molar ratio between the polycationic chitosan and lipophilic citral.

Low-Cost and Green Fabrication of Polymer Electronic Devices by Push-Coating of the Polymer Active Layers.

Because of both its easy processability and compatibility with roll-to-roll processes, polymer electronics is considered to be the most promising technology for the future generation of low-cost electronic devices such as light-emitting diodes and solar cells. However, the state-of-the-art deposition technique for polymer electronics (spin-coating) generates a high volume of chlorinated solution wastes during the active layer fabrication. Here, we demonstrate that devices with similar or higher performances can be manufactured using the push-coating technique in which a poly(dimethylsiloxane) (PDMS) layer is simply laid over a very small amount of solution (less than 1µL/covered cm2), which is then left for drying. Using mm thick PDMS provides a means to control the solvent diffusion kinetics (sorption/retention) and removes the necessity for additional applied pressure to generate the desired active layer thickness. Unlike spin-coating, push-coating is a slow drying process that induces a higher degree of crystallinity in the polymer thin film without the necessity for a post-annealing step. The polymer light-emitting diodes and solar cells prepared by push-coating exhibit slightly higher performances with respect to the reference spin-coated devices, whereas at the same time reduce the amounts of active layer materials and chlorinated solvents by 50 and 20 times, respectively. These increased performances can be correlated to the higher polymer crystallinities obtained without applying a post-annealing treatment. As push-coating is a roll-to-roll compatible method, the results presented here open the path to low-cost and eco-friendly fabrication of a wide range of emerging devices based on conjugated polymer materials.

Transfer-printing of active layers to achieve high quality interfaces in sequentially deposited multilayer inverted polymer solar cells fabricated in air.

Polymer solar cells (PSCs) are greatly influenced by both the vertical concentration gradient in the active layer and the quality of the various interfaces. To achieve vertical concentration gradients in inverted PSCs, a sequential deposition approach is necessary. However, a direct approach to sequential deposition by spin-coating results in partial dissolution of the underlying layers which decreases the control over the process and results in not well-defined interfaces. Here, we demonstrate that by using a transfer-printing process based on polydimethylsiloxane (PDMS) stamps we can obtain increased control over the thickness of the various layers while at the same time increasing the quality of the interfaces and the overall concentration gradient within the active layer of PSCs prepared in air. To optimize the process and understand the influence of various interlayers, our approach is based on surface free energy, spreading parameters and work of adhesion calculations. The key parameter presented here is the insertion of high quality hole transporting and electron transporting layers, respectively above and underneath the active layer of the inverted structure PSC which not only facilitates the transfer process but also induces the adequate vertical concentration gradient in the device to facilitate charge extraction. The resulting non-encapsulated devices (active layer prepared in air) demonstrate over 40% increase in power conversion efficiency with respect to the reference spin-coated inverted PSCs.

Poly(styrene)/oligo(fluorene)-intercalated fluoromica hybrids: synthesis, characterization and self-assembly.

We report on the intercalation of a cationic fluorescent oligo(fluorene) in between the 2D interlayer region of a fluoromica type silicate. The formation of intercalated structures with different fluorophore contents is observed in powders by synchrotron radiation XRD. Successively, the hybrids are dispersed in poly(styrene) through in situ polymerization. Such a procedure allows us to synthesize the materials from solution, to achieve solid films, and to characterize them by optical and morphologic techniques. The polymeric films with homogeneous distribution of the hybrids exhibit ultraviolet-blue photoluminescence with a significantly enhanced photostability compared to the bare oligo(fluorene)s. Finally, under specific conditions, the polymer hybrid with higher oligo(fluorene) content spontaneously assembles into highly ordered microporous films.

Enhanced Vertical Concentration Gradient in Rubbed P3HT:PCBM Graded Bilayer Solar Cells.

Graded bilayer solar cells have proven to be at least as efficient as the bulk heterojunctions when it comes to the Poly(3-hexylthiophene) (P3HT) - [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) donor-acceptor system. However, control of the vertical concentration gradient using simple techniques has never been reported. We demonstrate that rubbing the P3HT layer prior to PCBM deposition induces major morphological changes in the active layer. Using the newly introduced energy-dispersive X-ray spectroscopy element mapping technique, we found that rubbing P3HT induces the formation of an ideal vertical donor-acceptor concentration gradient. Furthermore, the P3HT crystallites undergo a molecular reorientation from edge-on to face-on configuration inducing a better charge transport in the vertical direction. The combination of these two major morphological changes leads to the fabrication of high-performance solar cells that exhibit, to date, the record efficiencies for spin-coated graded bilayers solar cells.

Thiophene based europium ß-diketonate complexes: effect of the ligand structure on the emission quantum yield.

The synthesis and the molecular and photophysical characterization, together with solid state and solution structure analysis, of a series of europium complexes based on ß-diketonate ligands are reported. The Eu(III) complex emission, specifically its photoluminescence quantum yield (PL-QY), can be tuned by changing ligands which finely modifies the environment of the metal ion. Steady-state and time-resolved emission spectroscopy and overall PL-QY measurements are reported and related to geometrical features observed in crystal structures of some selected compounds. Moreover, paramagnetic NMR, based on the analogous complexes with other lanthanides, are use to demonstrate that there is a significant structural reorganization upon dissolution, which justifies the observed differences in the emission properties between solid and solution states. The energy of the triplet levels of the ligands and the occurrence of nonradiative deactivation processes clearly account for the luminescence efficiencies of the complexes in the series.

Toward white light emission through efficient two-step energy transfer in hybrid nanofibers.

Nanosized zeolite L crystals containing about 550 strongly luminescent acceptor molecules have been modified by grafting a conjugated oligomer on their external surface. The 25 nm sized crystals have consequently been embedded in polymeric nanofibers obtained by electrospinning. The fluorescent molecule grafted on the external surface allows addressing the guests in the zeolite nanochannels through an efficient two-step energy transfer from the polymer nanofiber. The so obtained hybrid nanofibers exhibit intense emissions from the three fundamental colors using a single excitation wavelength. The molecule grafted on the external surface of the nanocrystal also induces a higher compatibility of the hybrid organic/inorganic nanomaterials in the conjugated polymer and therefore high concentrations of zeolites embedded in the nanofibers are obtained. Playing on this concentration, the emission of the nanofiber can be tuned and eventually be used for fabricating white-light emitting nanofibers. This hybrid nanomaterial opens new perspectives for low-cost nano organic light emitting diodes fabrication with considerable impact on the lighting and display technologies.

The role of triphenylamine in the stabilization of highly efficient polyfluorene-based OLEDs: a model oligomers study.

In order to understand the factors responsible for the improved efficiency and stability of organic light-emitting diodes (OLEDs) based on poly(9,9-dioctylfluorene) (PFO) when triphenylamine (TPA) is introduced as lateral fluorene substituent, we synthetize mono-disperse fluorene-thiophene oligomers as model compounds. Their blends with different concentrations of the fluorenone containing oligomer are studied in order to verify if only a reduction of ketonic defect sites or also an impeded energy transfer (ET) towards such sites are responsible for the suppression of the green emission band. We show that the introduction of TPA groups leads specifically both to an antioxidant action and a reduced ET towards residual defect sites, thanks to the environmental micro-encapsulation role played by TPA units surrounding the polymer backbone. As a result, the performances and colour stability of a device fabricated with TPA-substituted PFO (PFTPA) are strongly improved with respect to standard PFO device prepared in the same conditions.

Highly emissive nanostructured thin films of organic host-guests for energy conversion.

All-organic nanostructured host-guest systems, based on dyes inserted in the nanochannels of perhydrotriphenylene (PHTP) and deoxycholic acid (DCA), show enhanced fluorescence properties with quantum yields even higher than those of the dyes in solution, thanks to the high concentration of emissive molecules with controlled spatial and geometrical organization that prevents aggregation quenching. Both host molecules crystallize, growing with the long axis oriented along the direction of the nanochannels where the linear-chain dyes are inserted, to yield crystals emitting well-polarized light. For the DCA-based host-guests, homogeneous thin films suitable for several applications are obtained. Colour emission in such films can be tuned by co-inclusion of two or three dyes due to resonant energy-transfer processes. We show that films obtained by low-cost techniques, such as solution casting and spin-coating, convert UV light into visible light with an efficiency much higher than that of the standard polymeric blends.

Non-resonant z-scan characterization of the third-order nonlinear optical properties of conjugated poly(thiophene azines).

The nonlinear optical properties of a functionalized poly(thiophene azine), namely, poly(3,4-didodecylthiophene azine), PAZ, at the optical telecommunication wavelength of 1550 nm are investigated by means of the closed-aperture z-scan technique in both thin films and solutions. Values of chi((3))=(2.4+/-0.4)x10(-13) esu, n(2)=(4.0+/-0.7)x10(-15) cm(2) W(-1), and gamma=(4.5+/-0.7)x10(-34) esu are estimated for the third-order (Kerr) susceptibility, the intensity-dependent refractive index, and the molecular second hyperpolarizability of solution samples, respectively. A very small dependence on the polymer chain length is found. Markedly higher values of (4.4+/-1.1)x10(-11) esu, (6.6+/-1.0)x10(-13) cm(2) W(-1), and (5.0+/-0.8)x10(-33) esu are measured for the corresponding quantities in thick (up to 20 mum) polymer films cast on quartz plates. The enhancement of the NLO responses on going from solution to solid samples is attributed to a partially ordered structure and to the presence of interchain interactions leading to greater pi-electron delocalization in the cast polymer films. The results are compared with those previously obtained by using third-harmonic generation (THG), taking into account that those data were measured under conditions of three-photon resonance, whereas our z-scan measurements are fully off-resonance.

Field effect transistors with organic semiconductor layers assembled from aqueous colloidal nanocomposites.

We demonstrate field effect transistors based on organic semiconductor molecules dispersed in a self-organized polystyrene (PS) latex bead matrix. An aqueous colloidal composite made of PS and tetrahexylsexithiophene (H4T6) is deposited with a micropipet into the channel of a bottom-contact field effect transistor. The beads self-organize into a network whose characteristic distances are governed by their packing. The semiconductor molecules crystallize in the interstitial voids, leading to the growth of large interconnected domains. Depending on the bead size and the ratio between H4T6 and PS, the fraction of the different phases in the polymorph can be controlled. In the transistors where the H4T6 metastable "red phase" is the largest, the device response and the charge mobility are comparable to those of sexithienyl thin films grown by high-vacuum sublimation.