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Aggregation-induced emission (AIE), the phenomenon by which selected luminophores undergo the enhancement of emission intensity upon aggregation, has demonstrated potential in materials and biomaterials science, and in particular in those branches for which spectral management in the solid state is of fundamental importance. Its development in the area of luminescent spectral conversion devices like luminescent solar concentrators (LSCs) is instead still in its infancy. This account aims at summarizing relevant contributions made in this field so far, with a special emphasis on the design of molecular and macromolecular architectures capable of extending their spectral breadth to the deep-red (DR) and the near-infrared (NIR) wavelengths. Because of the many prospective advantages characterizing these spectral regions in terms of photon flux density and human-eye perception, it is anticipated that further development in the design, synthesis and engineering of advanced molecular and macromolecular DR/NIR-active AIE luminophores will enable faster and easier integration of LSCs into the built environment as highly transparent, active elements for unobtrusive light-to-electricity conversion.
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Poly(ionic liquid)s combine the unique properties of ionic liquids (ILs) within ionic polymers holding significant promise for energy storage applications. It is reported here the synthesis and characterization of a new family of poly(ionic liquid)s synthesized from cationic piperazinium ionic liquid monomers. The cationic poly(acrylamide piperazinium) in combination with sulfonamide anions like bis(trifluoromethanesulfonyl) imide (TFSI) and bis(fluorosulfonyl) imide (FSI) are characterized as solid polymer electrolytes. The polymer electrolytes in combination with pyrrolidonium ILs and LiFSI show high ionic conductivity, 5×10-3 S cm-1 at 100 °C. Piperazinium polymer electrolytes show excellent compatibility with lithium metal reversible plating and stripping at high current density and low temperature 40 °C.
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Suministros de Energía Eléctrica , Electrólitos , Líquidos Iónicos , Litio , Polímeros , Líquidos Iónicos/química , Litio/química , Electrólitos/química , Polímeros/química , Polímeros/síntesis química , Piperazinas/química , Estructura MolecularRESUMEN
In the last decades, chemists have developed methods to synthesize helical molecular architectures using a combination of covalent and non-covalent interactions. Very recently, the new class of completely covalent, one-handed helical ladder polymers has vigorously emerged. Such polymers can be rationally and programmably obtained through an approach guided by the principles of chirality-assisted-synthesis (CAS) and making use synergically of two disciplines that have so far rarely interacted: non-planar chiral π-conjugated synthons and ladder polymer chemistry. The precise programmability of the 3D structure and new mechanical and chiroptical properties will lead to potential applications in areas such as enantiorecognition, catalysis, spintronics and chiral-related optoelectronics. This minireview examines the emerging field of one-handed helical ladder polymers, analyzing their synthesis, applications, and limitations.
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Triptycene-based diiron(II) and dizinc(II) mesocates were obtained using a novel rigid ligand with two pyridylbenzimidazole chelating units fused into the triptycene scaffold. Studies on the diiron(II) assembly in solution showed that the complex undergoes thermal-induced one-step spin-crossover with T1/2 at 243 K (Evans method).
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The facile, metal-free synthesis and characterization of three new series of triptycene-fused pyridylbenzimidazoles are reported; such compounds possess an imidazole moiety fused within the benzene rings of the trypticene and a pyridine ring installed at position 2 of the imidazole rings. The position of the nitrogen atom of the pyridyl moiety linked to position 2 of the fused benzimidazole scaffold is systematically changed from the ortho to para position. The number of substituted blades bearing the pyridyl-substituted fused benzimidazole scaffolds has been increased from one to three. Such a library of compounds allowed us to evaluate the enhancement of two main effects: tautomeric isomerism and homoconjugation. The characteristic dynamic equilibrium between different isomers induced by prototropic tautomerization was examined by 1H nuclear magnetic resonance spectroscopy. By comparison of the photophysical properties of the new compounds with those of classical planar pyridylbenzimidazoles, the presence of the homoconjugation effect between the different triptycene blades was demonstrated. Fine details of the electronic structure of the new derivatives were unraveled by a computational analysis. The novel compounds can be employed for the construction of intriguing self-assembled supramolecular architectures.
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We present a divergent synthetic approach to C2-symmetrical 3,4-Ethylenedioxythiophene (EDOT) monomers in which functionalities can be introduced as pendant chains from the ethylene bridge. The key synthon, obtained through a high yielding trans-etherification, is the chiral EDOT with bromomethyl pendant groups and is prone to substitution reactions with oxygen-based nucleophiles. Elimination of the key precursor affords a diene that can be elaborated into unprecedented PhEDOT monomers using the Diels-Alder reaction. The strategy is further validated by the synthesis of a dithiane-containing EDOT.
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Alternating copolymers are distinctly unique in comparison with other copolymers. Herein, an in-depth investigation of the oxyanionic ring-opening copolymerization of propylene oxide (PO) and allyl glycidyl ether (AGE) from benzyl alcohol (BnOH) activated with potassium acetate (KOAc) complexed by 18-crown-6 ether (18C6) is described. We demonstrate that the 18C6/KOAc complex is an efficient and benign catalytic system to promote copolymerization of both oxirane monomers, leading to well-defined polyethers with varied comonomer content and low dispersity values (ÆM < 1.20). Kinetic analysis confirmed the controlled nature of the (co)polymerization process, and the determination of reactivity ratios revealed a quasi-alternating copolymerization profile, according to the Fineman-Ross method. The comparison between the quasi-alternating-type PO/AGE copolymerization and block or gradient copolymerization revealed significant differences, to confirm the different sequence incorporation in the different topological copolymers. These results highlight the great potential of 18C6/KOAc-mediated copolymerization process for the controlled sythesis of a series of copolymer topologies.
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Chiroptical materials are gaining increasing interest due to their innovative character and their applications in optoelectronics and data encryption technologies. Fully harnessing the potential of building blocks from the "chiral pool", such as native cyclodextrins (CDs), as they often lack chromophores suitable for the construction of materials with significant chiroptical properties. Here, we present the synthesis and characterization of a two-level molecular stack consisting of a point-chiral element (CD) and an axially chiral element (biphenyl), capable of effectively translating the overall stereochemical information contained in CDs into stimuli-responsive chiroptical properties. α- and ß-permethylated CDs were efficiently capped with two different 2,2'-difunctionalized 1,1'-biphenyl units. In CD derivatives containing the rigid 2,2'-dihydroxy-1,1'-biphenyl cap, two intramolecular hydrogen bonds act synergistically as stereoselective actuators, enabling effective communication between the two levels and the transfer of nonchromophoric stereochemical information from the cyclic-oligosaccharide to the atropoisomeric cap. The chiroptical properties can be finely tuned by external stimuli such as temperature and solvent. The way chirality is transferred from the CD platform to the biphenyl cap was revealed thanks to crystallographic and computational analyses, together with electronic circular dichroism (ECD) studies.
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We report the facile, metal-free convergent synthesis and the characterization of novel quinacridone dyes in which two triptycene units end-cap and sterically confine the quinacridone chromophore. A precise comparison of the confined dyes with their known homologues reveals that the reduction of π-π interactions in triptycene-fused quinacridone dyes compared to classical quinacridone results not only in an increase of solubility and processability but also in an enhancement of fluorescence quantum yield and photostability in the solid state.
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Layered Structures of Metal Ionic Polymers, or Ionic Polymer-Metal Composites (IPMCs) are formed by a membrane of an ionic electroactive materials flanked by two metal electrodes on both surfaces; they are devices able to change their shape upon application of an electrical external stimulus. This class of materials is used in various fields such as biomedicine, soft robotics, and sensor technology because of their favorable properties (light weight, biocompatibility, fast response to stimulus and good flexibility). With additive manufacturing, actuators can be customized and tailored to specific applications, allowing for the optimization of performance, size, and weight, thus reducing costs and time of fabrication and enhancing functionality and efficiency in various applications. In this review, we present an overview of the newest trend in using different 3D printing techniques to produce electrically responsive IPMC devices.
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In the past few decades, conjugated organic oligomers and polymers have been shown to have amazing properties, such as conductivity, which were traditionally considered counterintuitive for macromolecules consistently used as plastics and fibers (and thus, insulators) until the late 1970s [...].
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Plásticos , Polímeros , Sustancias Macromoleculares , Conductividad EléctricaRESUMEN
Realizing efficient all-polymer solar cell (APSC) acceptors typically involves increased building block synthetic complexity, hence potentially unscalable syntheses and/or prohibitive costs. Here we report the synthesis, characterization, and implementation in APSCs of three new polymer acceptors P1-P3 using a scalable donor fragment, bis(2-octyldodecyl)anthra[1,2-b : 5,6-b']dithiophene-4,10-dicarboxylate (ADT) co-polymerized with the high-efficiency acceptor units, NDI, Y6, and IDIC. All three copolymers have comparable photophysics to known polymers; however, APSCs fabricated by blending P1, P2 and P3 with donor polymers PM5 and PM6 exhibit modest power conversion efficiencies (PCEs), with the champion P2-based APSC achieving PCE=5.64 %. Detailed morphological and microstructural analysis by AFM and GIWAXS reveal a non-optimal APSC active layer morphology, which suppresses charge transport. Despite the modest efficiencies, these APSCs demonstrate the feasibility of using ADT as a scalable and inexpensive electron rich/donor building block for APSCs.
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We report on the synthesis and characterization of a novel class of hyperbranched polymers, in which a copper(I)-catalyzed alkyne azide cycloaddition (CuAAC) reaction (the prototypical "click" reaction) is used as the polymerization step. The AB2 monomers bear two azide functionalities and one alkyne functionality, which have been installed onto a 1,3,5 trisubstituted benzene aromatic skeleton. This synthesis has been optimized in terms of its purification strategies, with an eye on its scalability for the potential industrial applications of hyperbranched polymers as viscosity modifiers. By taking advantage of the modularity of the synthesis, we have been able to install short polylactic acid fragments as the spacing units between the complementary reactive azide and alkyne functionalities, aiming to introduce elements of biodegradability into the final products. The hyperbranched polymers have been obtained with good molecular weights and degrees of polymerization and branching, testifying to the effectiveness of the synthetic design. Simple experiments on glass surfaces have highlighted the possibility of conducting the polymerizations and the formation of the hyperbranched polymers directly in thin films at room temperature.
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Azidas , Polímeros , Polimerizacion , Alquinos , CobreRESUMEN
Hexasubstituted benzenes are interesting platforms for the generation of functional materials, whose applications span from supramolecular recognition to organic electronics. Their synthesis is difficult to achieve by controlling multiple substitution steps of all hydrogen atoms on the aromatic benzene skeleton, so, often, cycloaddition reactions from disubsituted alkynes are used. In this work, we report a novel, straightforward route to C3-symmetrical hexasubstituted aromatic synthons with a diverse and rich pattern of functionalities, and we report about their packing mode in the crystals, in which, unprecedentedly, directional, strong halogen bonding interactions are capable of forming bidimensional supramolecular weaving.
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The chiral resolving ability of the commercially available amylose (3,5-dimethylphenylcarbamate)-based chiral stationary phase (CSP) toward four chiral probes representative of four kinds of stereogenicity (central, axial, helical, and planar) was investigated. Besides chirality, the evident structural feature of selectands is an extremely limited conformational freedom. The chiral rigid analytes were analyzed by using pure short alcohols as mobile phases at different column temperatures. The enantioselectivity was found to be suitable for all compounds investigated. This evidence confirms that the use of the amylose-based CSP in HPLC is an effective strategy for obtaining the resolution of chiral compounds containing any kind of stereogenic element. In addition, the experimental retention and enantioselectivity behavior, as well as the established enantiomer elution order of the investigated chiral analytes, may be used as key information to track essential details on the enantiorecognition mechanism of the amylose-based chiral stationary phase.
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Alcoholes , Amilosa , Amilosa/química , Estereoisomerismo , Cromatografía Líquida de Alta Presión , Fenilcarbamatos/químicaRESUMEN
This paper studies the mechanism of electrochemically induced carbon-bromine dissociation in 1-Br-2-methylnaphalene in the reduction regime. In particular, the bond dissociation of the relevant radical anion is disassembled at a molecular level, exploiting quantum mechanical calculations including steady-state, equilibrium and dissociation dynamics via dynamic reaction coordinate (DRC) calculations. DRC is a molecular-dynamic-based calculation relying on an ab initio potential surface. This is to achieve a detailed picture of the dissociation process in an elementary molecular detail. From a thermodynamic point of view, all the reaction paths examined are energetically feasible. The obtained results suggest that the carbon halogen bond dissociates following the first electron uptake follow a stepwise mechanism. Indeed, the formation of the bromide anion and an organic radical occurs. The latter reacts to form a binaphthalene intrinsically chiral dimer. This paper is respectfully dedicated to Professors Anny Jutand and Christian Amatore for their outstanding contribution in the field of electrochemical catalysis and electrosynthesis.
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Bromo , Carbono , Aniones , Bromo/química , Carbono/química , Electrones , NaftalenosRESUMEN
The oxyanionic ring-opening polymerization of propylene oxide (PO) from an exogenous alcohol activated with benign (complexed) metal-alkali carboxylates is described. The equimolar mixture of potassium acetate (KOAc) and 18-crown-6 ether (18C6) is demonstrated to be the complex of choice for preparing poly(propylene oxide) (PPO) in a controlled manner. In the presence of 18C6/KOAc, hydrogen-bonded alcohols act as soft nucleophiles promoting the PO SN 2 process at room temperature and in solvent-free conditions while drastically limiting the occurrence of parasitic hydrogen abstraction generally observed during the anionic ROP of PO. The resulting PPO displays predictable and unprecedented molar masses (up to 20 kg mol-1 ) with low dispersities (DM < 1.1), rendering the 18C6/KOAc complex the most performing activator for the oxyanionic polymerization of PO reported to date. Preliminary studies on the preparation of block and statistical copolyethers are also reported.
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Compuestos Epoxi , Acetato de Potasio , Polimerizacion , Catálisis , Hidrógeno , ÁlcalisRESUMEN
A chiral cage is proposed as an effective chiroptical sensor for perrhenate (surrogate for 99TcO4-) in water, fruit juice and artificial urine media. The key mechanism for the chiroptical sensing resides in the change of dihedral angle of the binaphthyl unit and H-bonds with the guest, resulting in ample changes of the CD signal as a consequence of the binding event.
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Renio , AguaRESUMEN
Two chiral triptycene derivatives were analyzed on the Chiralpak IB-U column packed with cellulose tris(3,5-dimethylphenylcarbamate)-based sub-2-µm diameter particles. Under normal-phase conditions, sub-minute baseline enantioseparations were obtained. Differences in structural elements and chromatographic behavior of the investigated compounds were evaluated to identify the interactions that drive the chiral discrimination process. From the evaluation of the experimental chromatographic data, it was found that hydrogen bond formation is essential for the separation of enantiomers.
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Herein, we report the synthesis and characterization of homochiral macrocycles, in which molecular rigidity, combined with the presence of multiple functional groups, allow for the assembly of helical nanostructures. 1,1'-bi-2-naphthol (Binol) units are used as robust chirality inducers, and pyridyl units embedded within the molecular frameworks allow the assembly, upon coordination with Pd(II) metal ions, of the macrocyclic building blocks. CD and NMR spectroscopies show the formation of ordered 1D assembly in solution. AFM studies indicate that the molecular systems are capable of forming nanoscale structures. The effective transfer of chiral information results in helical nanofibers, with lengths ranging from a few hundreds of nanometers to some micrometers. AFM line profiles reveal a helical longitudinal period of about 50â nm and a transverse width of 25 to 45â nm after deconvolution.