RESUMO
Redox-conducting polymers based on SalEn-type complexes have attracted considerable attention due to their potential applications in electrochemical devices. However, their charge transfer mechanisms, physical and electrochemical properties remain unclear, hindering their rational design and optimization. This study aims to establish the influence of monomer geometry on the polymer's properties by investigating the properties of novel nonplanar SalEn-type complexes, poly[N,N'-bis(salicylidene)propylene-2-(hydroxy)diaminonickel(II)], and its analog with 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-substituted bridge (MTS). To elucidate the charge transfer mechanism, operando UV-Vis spectroelectrochemical analysis, electrochemical impedance spectroscopy, and electron paramagnetic resonance are employed. Introducing TEMPO into the bridge moiety enhanced the specific capacity of the poly(MTS) material to 95 mA h g-1, attributed to TEMPO's and conductive backbone's charge storage capabilities. Replacement of the ethylenediimino-bridge with a 1,3-propylenediimino- bridge induced significant changes in the complex geometry and material's morphology, electrochemical, and spectral properties. At nearly the same potential, polaron and bipolaron particles emerged, suggesting intriguing features at the overlap point of the electroactivity potentials ranges of polaron-bipolaron and TEMPO, such as a disruption in the connection between TEMPO and the conjugation chain or intramolecular charge transfer. These results offer valuable insights for optimizing strategies to create organic materials with tailored properties for use in catalysis and battery applications.
Assuntos
Óxidos N-Cíclicos , Oxirredução , Polímeros , Óxidos N-Cíclicos/química , Polímeros/química , Polímeros/síntese química , Etilenodiaminas/química , Estrutura Molecular , Técnicas Eletroquímicas , Condutividade ElétricaRESUMO
A family of coordination polymers (CPs) based on dynamic structural elements are of great fundamental and commercial interest addressing modern problems in controlled molecular separation, catalysis, and even data processing. Herein, the endurance and fast structural dynamics of such materials at ambient conditions are still a fundamental challenge. Here, we report on the design of a series of Cu-based CPs [Cu(bImB)Cl2] and [Cu(bImB)2Cl2] with flexible ligand bImB (1,4-bis(imidazol-1-yl)butane) packed into one- and two-dimensional (1D, 2D) structures demonstrating dimensionality mediated flexibility and reversible structural transformations. Using the laser pulses as a fast source of activation energy, we initiate CP heating followed by anisotropic thermal expansion and 0.2-0.8% volume changes with the record transformation rates from 2220 to 1640 s-1 for 1D and 2D CPs, respectively. The endurance over 103 cycles of structural transformations, achieved for the CPs at ambient conditions, allows demonstrating optical fiber integrated all-optical data processing.
RESUMO
We demonstrate herein an all-optical switch based on stimuli-responsive and photochromic-free metal-organic framework (HKUST-1). Ultrafast near-infrared laser pulses stimulate a reversible 0.4â eV blue shift of the absorption band with up to 200â s-1 rate due to dehydration and concomitant shrinking of the structure-forming [Cu2 C4 O8 ] cages of HKUST-1. Such light-induced switching enables the remote modulation of intensities of photoluminescence of single crystals of HKUST-1 as well visible radiation passing through the crystal by 2 order of magnitude. This opens up the possibility of utilyzing stimuli-responsive MOFs for all-optical data processing devices.
RESUMO
This study aimed to identify the optimum printing parameters for the fused filament fabrication (FFF) of acrylonitrile butadiene styrene (ABS) and polyamide (nylon), to improve strength properties. For this purpose, the methodology of the paper involves an experimental study that used Taguchi's method to identify the effects of the infill pattern, infill density, and printing speed on the mechanical properties of the materials. ABS and nylon plastic parts were tested in tension to failure. Based on the results of the tensile tests, it was found that ABS material produced the highest ultimate tensile strength when printed using a tri-hexagonal infill pattern, 100% infill density, and a printing speed of 65 mm/s. On the other hand, nylon material exhibited a better performance when printed using an octet geometric structure, with identical other parameters.
RESUMO
Polymers with embedded metal-organic frameworks (MOFs) have been of interest in research for advanced applications in gas separation, catalysis and sensing due to their high porosity and chemical selectivity. In this study, we utilize specific MOFs with high thermal stability and non-centrosymmetric crystal structures (zeolitic imidazolate framework, ZIF-8) in order to give an example of MOF-polymer composite applications in nonlinear optics. The synthesized MOF-based polymethyl methacrylate (PMMA) composite (ZIF-8-PMMA) demonstrates the possibility of the visualization of near-infrared laser beams in the research lab. The resulting ZIF-8-PMMA composite is exposed to a laser under extreme conditions and exhibits enhanced operating limits, much higher than that of the widely used inorganic materials in optics. Overall, our findings support the utilization of MOFs for synthesis of functional composites for optical application.