ABSTRACT
In this study, polyvinylpyrrolidone (PVP) was introduced into an Ag deposition-based electrochromic (EC) device as a capping agent for electrodeposited Ag nanoparticles (AgNPs) to improve the coloration characteristics of EC devices and to precisely control the size and shape of the AgNPs. Through the coordination of PVP molecules with Ag+ ions in the EC electrolyte, the critical voltage for the deposition of AgNPs decreased, resulting in a lower operating voltage of the EC device in comparison with the conventional one. Because particle growth and AgNP aggregation were suppressed by the capping effect of PVP, uniform electrodeposition of AgNPs was achieved. Aggregation suppression enabled vivid cyan, yellow, and red coloration using a simple driving procedure. The suppression of AgNP aggregation by PVP was demonstrated even in an electrochemical system. Furthermore, the capping effect of PVP also improved image retention. Better color retention properties were achieved even without the use of any counter-modified electrode cells.
ABSTRACT
This study investigates the electrochemical modulation of luminescence color, i.e., electrofluorochromism, of an Eu complex in a polyether solvent. The electrofluorochromic (EFC) reaction of the Eu complex occurred via a reversible redox reaction between Eu3+ and Eu2+. Initially, the intrinsically stable Eu3+ complex showed intense red photoluminescence (PL) induced by f-f transitions. After the electrochemical reduction of Eu3+ to Eu2+, broad blue PL was observed attributed to the d-f transitions in the Eu2+ complex. This distinct blue luminescence from the Eu2+ complex was attributed to the effective stabilization of the Eu2+ state by the polyether solvent. The dynamic EFC reaction that changes the valence state of the Eu ion can be potentially applied to novel chemical sensors, security devices, and display devices.
ABSTRACT
Electrochemical switching of luminescence color between magenta and blue using two types of luminescent materials and electrochromic molecules was demonstrated based on the control of excited energy transfer through an electrochromic reaction. The magenta photoluminescence, due to the integration of red luminescence from the Eu(III) complex and blue fluorescence from the anthracene derivative, was reversibly modulated to a pure-blue luminescence color by an electrochemical redox reaction. Electrofluorochromism is induced by effective excited energy transfer from the Eu(III) complex to the electrochromic molecule under a redox reaction.
ABSTRACT
The front cover artwork is provided by the group of Norihisa Kobayashi and Kazuki Nakamura at Chiba University. The image shows the drastic luminescence enhancement and induced circular polarization of Eu(D-facam)3 in the presence of tetramethylammonium acetate. Read the full text of the Article at 10.1002/cphc.202100609.
ABSTRACT
The effect of a series of tetramethylammonium salts with different counter anions on the photophysical properties of a chiral Eu(III) complex (Eu(D-facam)3 ) was investigated. Anion-dependent luminescence of the Eu(III) complex was observed, and particularly in the presence of acetate ions, an outstanding luminescence enhancement (>300â times) and induced circularly polarized luminescence (glum =-0.63) were obtained. The energy transfer process was then evaluated using key photophysical parameters, and it was found that the sensitisation efficiency of the Eu(III) complex significantly increased in the presence of tetramethylammonium acetate (TMAOAc). The interactions between Eu(D-facam)3 and TMAOAc were confirmed by luminescence analysis, circular dichroism spectroscopy, Fourier transform infrared spectroscopy and mass spectral measurements.
ABSTRACT
DNA-based materials have attracted much attention due to their unique photo-functional properties and potential applications in various fields such as luminescent and biological systems, nanodevices, etc. In this study, the photophysical properties of a chiral Eu(III) complex, namely (Eu(D-facam)3), within DNA films were extensively investigated. The enhancement of photoluminescence (more than 25-folds increase of luminescence quantum yield) and degree of circularly polarization in luminescence (glum = - 0.6) was observed upon interaction with DNA. Various photophysical analyses suggested that the emission enhancement was mainly due to an increase of the sensitization efficiency (high ηsens) from the ligands to Eu(III) and suppression of the vibrational deactivation upon immobilization onto the DNA molecule. From CD and VCD measurements, it was suggested that the coordination structure of Eu(D-facam)3 was affected by the interaction with DNA, suggesting that the structural change of Eu(D-facam)3 contributed to the improvement of its luminescent properties.
Subject(s)
Cetrimonium/chemistry , DNA/chemistry , Europium/chemistry , Circular Dichroism , Crystallography, X-Ray , Fluorescence , StereoisomerismABSTRACT
Ag nanoparticles exhibit various colors depending on their localized surface plasmon resonance (LSPR). Based on this phenomenon, Ag deposition-based electrochromic devices can represent various optical states in a single device such as the three primary colors (cyan, magenta, and yellow), silver mirror, black and transparent. A control of the morphology of Ag nanoparticles can lead to dramatic changes in color, as their size and shape influence the LSPR band. In this research, we focused on the diffusion rate of Ag+ ions when Ag nanoparticles are electrochemically deposited. Consequently, well-isolated Ag nanoparticles were obtained due to the slow growth rate by using an electrolyte with a low concentration of Ag+ ions, resulting in an improvement in the color quality of cyan and magenta. Additionally, spherical Ag nanoparticles were deposited in the same device by optimizing their voltage application conditions, which represented yellow and green colors. In particular, green coloration is a unique phenomenon because it can appear by the combination of two absorption peaks of LSPR. As a result of investigating the finite-difference time-domain method, it was observed that the LSPR band in the long wavelength region was originated from the effects of the connection between Ag particles.
ABSTRACT
Drastic enhancements in both emission intensity and circular polarization of a Eu(iii) complex were achieved in 1-butanol solution in the presence of alkylammonium ions.
ABSTRACT
We describe here the preparation of soft crystals using disilanyl macrocycle C4 possessing four p-phenylenes circularly connected by four flexible disilane bonds. Single crystals of C4 exhibited a reversible thermal single-crystal-to-single-crystal (SCSC) phase transition behavior between two crystal phases accompanied by remarkable mechanical motion (thermosalient effect), as revealed by thermal analyses and X-ray diffraction measurements. Detailed structural analyses implied that flexibility of the parallelogram disilanyl architecture and molecular packing mode via weak intermolecular interactions facilitated a concerted structural transformation (parallel crank motion) of macrocycles in the crystal, thus resulting in the SCSC phase transition accompanied by anisotropic shrinking/elongation of the cells to induce the thermosalient effect. This work explores a new area of organosilicon chemistry and presents the potential utility of disilanyl macrocycles as soft crystals.
ABSTRACT
Organic nonvolatile transistor memory with synthetic polypeptide derivatives as dielectric was fabricated by a solution process. When only poly (γ-benzyl-l-glutamate) (PBLG) was used as dielectric, the device did not show obvious hysteresis in transfer curves. However, PBLG blended with PMMA led to a remarkable increase in memory window up to 20 V. The device performance was observed to remarkably depend on the blend ratio. This study suggests the crystal structure and the molecular alignment significantly affect the electrical performance in transistor-type memory devices, thereby provides an alternative to prepare nonvolatile memory with polymer dielectrics.
Subject(s)
Equipment Design/methods , Nanostructures/chemistry , Peptides/chemistry , Polyglutamic Acid/analogs & derivatives , Polymers/chemistry , Polymethyl Methacrylate/chemistry , Transistors, Electronic , Circular Dichroism , Computer Storage Devices , Electricity , Microscopy, Atomic Force , Polyglutamic Acid/chemistry , Surface Properties , X-Ray DiffractionABSTRACT
Electrochemically triggered upconverted luminescence through triplet-triplet energy transfer (TTET) and subsequent triplet-triplet annihilation upconversion (TTA-UC) is observed for the first time in the electrochemiluminescence properties of a Ru(bpy)32+/DPA-containing electrochemical device.
ABSTRACT
Despite the application of electrochromic (EC) technologies in various optical modulating devices, the challenge to achieve multicolour EC behavior in a single device still remains. However, because almost all EC materials exhibit a single colour change, only a few organic materials are able to undergo multiple colour switching within a single device. The development of multicolour EC applications is therefore highly limited. In this research, we fabricated an EC device (ECD) with the simple hybrid capacitor architecture, i.e. with a flat ITO electrode as the working side and an ITO particle-modified electrode as the counter side. We also employed an electrolyte containing both anodic and cathodic EC materials consisting of small organic molecules. In this novel ECD, each EC material successfully undergoes individual colour switching from light yellow to light green and magenta. The mechanism of a multicolour system represents a significant breakthrough towards a full-colour ECD, thereby expanding the potential of EC technology.
ABSTRACT
Electrochemiluminescence (ECL) refers to light emission induced by an electrochemical redox reaction. The stability, emission response, and light intensity of the ECL device are known to be improved by using an alternating current (AC) voltage. In this paper, an AC-driven ECL device is fabricated with DNA/Ru(bpy)32+ hybrid film-modified electrode. The Ru(bpy)32+ complex exhibits significant electrochemical reactivity in the DNA/Ru(bpy)32+ hybrid film prepared by electrochemical adsorption. The hybrid film contains unique micrometre-scale aggregates of Ru(bpy)32+ in DNA matrix. The physicochemical properties of the hybrid film and its AC-driven ECL characteristics in the electrochemical device are studied. Orange-coloured ECL is observed to be emitted from only the aggregated structures in the hybrid film at the high AC frequency of 10 kHz, which corresponds to a response time shorter than 100 µs.
ABSTRACT
The electroresponsive switching of red photoluminescence based on the electrochemical coloration of cyan-magenta-green (CMG) viologen components was achieved by combining a luminescent Eu3+ chelate and viologen derivatives, resulting in CMG coloration in a single cell. The cell coloration was controlled by an electrochromic (EC) reaction, which also modulated the photoluminescence of the Eu3+ chelate with high contrast, by transferring energy from the excited state of the Eu3+ ion to the colored states of EC molecules. Cyclic voltammograms, photoluminescence spectra, absorption spectra, luminescence quantum yields, and luminescence lifetimes were measured to clarify the differences between the luminescence quenching and energy transfer efficiencies for each C, M, and G coloration associated with the electrochromism. Thus, the spectral overlap between the luminescence band of the Eu3+ chelate and the absorption band of the colored EC molecules was proven to affect the efficiency of luminescence modulation.
ABSTRACT
Electrochemiluminescence (ECL) is a phenomenon in which light is emitted from the excited state of a redox-active material generated by electrochemical reactions. Among light-emitting devices, ECL devices have various advantages in terms of structure and ease of fabrication, and therefore, they are expected to be next-generation emitting devices. In this study, we introduced rutile-type titanium dioxide nanoparticles (TiO2 NPs) in a Ru(ii)-complex-based electrolyte to improve the emission properties of an alternating current (AC)-driven ECL device. The properties of the ECL device with TiO2 NPs were greatly improved (emission luminescence, 165 cd m(-2); half-life time, 1000 s) compared to a previously reported AC-driven ECL device without nanoparticles. To determine how TiO2 NPs helped in achieving high emission luminescence and long-term stability, we measured the optical and electrochemical properties of the Ru(bpy)3(2+)-based ECL solution in detail. The PL intensity of Ru(bpy)3(2+) was increased by adding TiO2 NPs, which indicated that the suppression of non-radiative quenching of the complex's excited states could improve the ECL intensity. With respect to the enhanced stability, electron transfers between Ru(bpy)3(2+) and TiO2 were suggested by detailed electrochemical measurements. These electron transfers occurred from the reduced Ru(bpy)3(2+) species to the TiO2, and subsequently, from the TiO2 to the oxidized Ru(bpy)3(2+) species. Such electron transfers are thought to improve the balance of the redox reactions in the ECL device, leading to long-term stability.
ABSTRACT
Multifunctional electroswitching of both emission and coloration was demonstrated by using fluoran derivatives in an electrolytic solution. Further, in order to investigate changes in the photophysical properties induced by electrical stimuli, we measured cyclic voltammogram, absorption spetra, emission spectra, and molecular orbital calculation. The mechanism for this electroswitching was attributed to the reversible electrochemically induced closing and opening of the lactone ring in the fluoran molecule. All neutral fluoran molecules were colorless and did not exhibit any fluorescence, while the oxidized (lactone ring-opened form) molecule was yellow and displayed a green fluorescence as a consequence of the extended, planar, conjugated system. Furthermore, this fluoran molecule achieved reversible electroswitchable emission and coloration with high on/off contrast.
Subject(s)
Fluoresceins/chemistry , Computer Simulation , Electrolytes/chemistry , Fluorescence , Models, Chemical , Molecular Structure , Oxidation-Reduction , Solutions , Spectrum AnalysisABSTRACT
The first localized surface plasmon resonance (LSPR)-based multicolor electrochromic device with five reversible optical states is demonstrated. In this device, the size of deposited silver nanoparticles is electrochemically controlled by using a voltage-step method in which two different voltages are applied successively. The electrochemically size-controlled silver nanoparticles enable a reversible multiple-color change by a shift of the LSPR band.
Subject(s)
Metal Nanoparticles/chemistry , Silver/chemistry , Electrochemical Techniques , Electrodes , Surface Plasmon Resonance , Tin Compounds/chemistryABSTRACT
No fade to grey: Electroswitching of emission and coloration was achieved for a combination of a luminescent Eu(III) complex and an electrochromic molecule of diheptyl viologen (HV(2+)), indicating that such a combination could be used as a display material with dual emissive and reflective modes. The Prussian blue (PB)-modified electrode improved the response time and reversibility for the switching of emission and coloration, by acting as a counter electrode for the electrochromism of HV(2+).
Subject(s)
Electrochemical Techniques , Coordination Complexes/chemistry , Electrodes , Europium/chemistry , Ferrocyanides/chemistry , Fluorescence Resonance Energy Transfer , Fluorescent Dyes/chemistryABSTRACT
We studied the electrochromic (EC) and electrochemiluminescent (ECL) properties of a novel dual-mode display (DMD) cell that was enabled for reflective and emissive modes of representation by introducing both EC and ECL materials into an electrochemical cell. We fabricated EC, ECL, and DMD cells based on a simple-mixture solution or modified electrodes and compared their properties to clarify the advantage of a DMD system based on modified electrodes. Both the solution- and modified electrode-based DMDs showed EC properties in the reflective mode under dc bias application and ECL properties in the emissive mode under ac bias application. Although the solution-based DMD cell featured a very simple structure, some improvements related to side reaction and quenching reaction were required. The modified electrode-based DMD cell was fabricated to improve these aspects. The advantage of the DMD model based on the modified electrodes was certainly suggested by comparisons of the results with those of EC, ECL, and DMD cells based on a simple-mixture solution.