Effect of the electron donating group on the excited-state electronic nature and epsilon-near-zero properties of curcuminoid-borondifluoride dyes.

Epsilon-near-zero (ENZ) properties have been reported in organic molecular films. In particular, cyanine and squaraine films have been shown to exhibit ENZ properties in the visible spectral region with a strong 3rd order nonlinear optical response near the ENZ spectral region. Noting both cyanine and squaraine belong to the polymethine family, a series of six curcuminoid borondifluoride (Curc) derivatives were developed to examine whether such a polymethine character is positively correlated with the ENZ property of the organic films. Those Curc derivatives possess a Donor-Acceptor-Donor (D-A-D) architecture with acceptor, AcacBF2, located at the molecular center. The backbone of Curc is designed such that the donor strength can be tuned to transit between charge transfer (CT) and polymethine character. This balance between CT and polymethine character of the Curc series is examined based on the Lippert-Mataga plot. As donor strength in the D-A-D structure increases, CT character is less marked resulting in a more dominant polymethine character. The structural and optical properties of the Curc films with a thickness in the order of 30 nm were examined to correlate the polymethine character with the ENZ response. The results obtained in isotropic Curc thin films demonstrate that an increase of polymethine character associated with a stronger donor strength leads to an appearance/enhancement of the ENZ property in the visible spectrum range from 500 to 670 nm. Overall, this study provides useful guidelines to engineer new organic materials showing ENZ properties in a desired spectral range.

σ-Conjugation and H-Bond-Directed Supramolecular Self-Assembly: Key Features for Efficient Long-Lived Room Temperature Phosphorescent Organic Molecular Crystals.

Long-lived room temperature phosphorescence from organic molecular crystals attracts great attention. Persistent luminescence depends on the electronic properties of the molecular components, mainly π-conjugated donor-acceptor (D-A) chromophores, and their molecular packing. Here, a strategy is developed by designing two isomeric molecular phosphors incorporating and combining a bridge for σ-conjugation between the D and A units and a structure-directing unit for H-bond-directed supramolecular self-assembly. Calculations highlight the critical role played by the two degrees of freedom of the σ-conjugated bridge on the chromophore optical properties. The molecular crystals exhibit RTP quantum yields up to 20 % and lifetimes up to 520 ms. The crystal structures of the efficient phosphorescent materials establish the existence of an unprecedented well-organization of the emitters into 2D rectangular columnar-like supramolecular structure stabilized by intermolecular H-bonding.

Terahertz optical characteristics of two types of metamaterials for molecule sensing.

We investigate spectral responses of two different terahertz (THz) metamaterials of double split ring resonator (DSRR) and the nano slot resonator (NSR) for molecule sensing in low concentration. Two different resonant frequencies of DSRR can be controlled by polarization angle of incident THz beam. For comparison of THz optical characteristics, two NSRs were made as showing the same resonant frequencies as DSRR's multimode. The monosaccharide molecules of glucose and galactose were detected by these two types of metamaterials matching the resonant frequencies in various concentration. NSR shows higher sensitivity in very low concentration range rather than DSRR, although the behavior was easily saturated in terms of concentration. In contrast, DSRR can cover more broad concentration range with clear linearity especially under high quality factor mode in polarization of 67.5 degree due to the Fano resonance. THz field enhancement distributions were calculated to investigate sensing performance of both sensing chips in qualitative and quantitative manner.

Blue-Shifting Intramolecular Charge Transfer Emission by Nonlocal Effect of Hyperbolic Metamaterials.

Metallic nanostructures permit controlling various photophysical processes by coupling photons with plasmonic oscillation of electrons confined in the tailored nanostructures. One example is hyperbolic metamaterial (HMM) leading to an enhanced spontaneous emission rate of emitters located nearby. Noting that emission in organic molecules is from either π-π* or intramolecular charge-transfer (ICT) states, we address here how HMM modifies ICT emission spectral features by comparing them with a spectral shift dependent on the local polarity of the medium. The 7.0 nm blue shift is observed in ICT emission from 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran dispersed into a polymer matrix prepared on HMM multilayered structure, while no spectral shift is observed in π-π* emission from perylene diimide. In the frame of the Lippert-Mataga formalism, the blue shift is explained by the HMM nonlocal effects resulting from 8% decrease in refractive index and 18% reduction in dielectric permittivity. This phenomenon was also shown in a hemicurcuminoid borondifluoride dye yielding 15.0 nm blue shift. Such a capability of spectral shift control in films by HMM structure opens new prospects for engineering organic light-emitting devices.

Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues.

Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene:perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7-that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal-dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.

Strong Light Confinement in Metal-Coated Si Nanopillars: Interplay of Plasmonic Effects and Geometric Resonance.

We investigated the influence of metal coating on the optical characteristics of Si nanopillar (NP) arrays with and without thin metal layers coated on the sample surface. The reflection dips of the metal-coated arrays were much broader and more pronounced than those of the bare arrays. The coated metal layers consisted of two parts-the metal disks on the Si NP top and the holey metal backreflectors on the Si substrate. The Mie-like geometrical resonance in the NPs, the localized surface plasmons in the metal disks, and the propagation of surface plasmon polariton along the backreflector/substrate interface could contribute to the reflection spectra. Finite-difference time-domain simulation results showed that the interplay of the plasmonic effects and the geometric resonance gave rise to significantly enhanced light confinement and consequent local absorption in the metal-Si hybrid nanostructures.

Borondifluoride complexes of hemicurcuminoids as bio-inspired push-pull dyes for bioimaging.

Hemicurcuminoids are based on half of the π-conjugated backbone of curcuminoids. The synthesis of a series of such systems and their borondifluoride complexes is described. The electrochemical and photophysical properties of difluorodioxaborine species were investigated as a function of the nature of electron donor and acceptor groups appended at either terminal positions of the molecular backbone. The emissive character of these dipolar dyes was attributed to an intraligand charge transfer process, leading to fluorescence emission that is strongly dependent on solvent polarity. Quasi-quantitative quenching of fluorescence in high polarity solvents was attributed to photoinduced electron transfer. These dyes were shown to behave as versatile fluorophores. Indeed, they display efficient two-photon excited fluorescence emission leading to high two-photon brightness values. Furthermore, they form nanoparticles in water whose fluorescence emission quantum yield is less than that of the dye in solution, owing to aggregation-induced fluorescence quenching. When cos7 living cells were exposed to these weakly-emitting nanoparticles, one- and two-photon excited fluorescence spectra showed a strong emission within the cytoplasm that originated from the individual molecules. Dye uptake thus involved a disaggregation mechanism at the cell membrane which restored fluorescence emission. This off-on fluorescence switching allows a selective optical monitoring of those molecules that do enter the cell, which offers improved sensitivity and selectivity of detection for bioimaging purposes.

Tuning the Direction of Intramolecular Charge Transfer and the Nature of the Fluorescent State in a T-Shaped Molecular Dyad.

Controlling photoinduced intramolecular charge transfer at the molecular scale is key to the development of molecular devices for nanooptoelectronics. Here, we describe the design, synthesis, electronic characterization, and photophysical properties of two electron donor-acceptor molecular systems that consist of tolane and BF2-containing curcuminoid chromophoric subunits connected in a T-shaped arrangement. The two π-conjugated segments intersect at the electron acceptor dioxaborine core. From steady-state electronic absorption and fluorescence emission, we find that the photophysics of the dialkylamino-substituted analogue is governed by the occurrence of two closely lying excited states. From DFT calculations, we show that excitation in either of these two states results in a distinct shift of the electron density, whether it occurs along the curcuminoid or tolane moiety. Femtosecond transient absorption spectroscopy confirmed these findings. As a consequence, the nature of the emitting state and the photophysical properties are strongly dependent on solvent polarity. Moreover, these characteristics can also be switched by protonation or complexation at the nitrogen atom of the amino group. These features set new approaches toward the construction of a three-terminal molecular system in which the lateral branch would transduce a change of electronic state and ultimately control charge transport in a molecular-scale device.

Electro-optic switching in metamaterial by liquid crystal.

Electro-optic switching of reflection and refraction is experimentally demonstrated in metasurface liquid crystal cell. Negative metasurface is fabricated by focused-ion-beam milling, and twisted nematic cells are constructed with complementary double-split ring resonator and V-shape slot antenna metasurface. By application of an external voltage, electro-optic switchings are achieved in reflection and refraction. It has a strong implication for applications in spatial light modulation and wavelength division multiplexer/demultiplexer in a near-IR spectral range.

Temporal, thermal, and light stability of continuously tunable cholesteric liquid crystal laser array.

Fine-structured polymerized cholesteric liquid crystal (PCLC) wedge laser devices have been realized, with high fine spatial tunability of the lasing wavelength. With resolution less than 0.3 nm in a broad spectral range, more than one hundred laser lines could be obtained in a PCLC cell without extra devices. For practical device application, we studied the stability of the device in detail over time, and in response to strong external light sources, and thermal perturbation. The PCLC wedge cells had good temporal stability for 1 year and showed good stability for strong perturbations, with the lasing wavelength shifting less than 1 nm, while the laser peak intensities decreased by up to 34%, and the high energy band edge of the photonic band gap (PBG) was red shifted 3 nm by temperature perturbation. However, when we consider the entire lasing spectrum for the PCLC cell, the 1-nm wavelength shift may not matter. Although the laser peak intensities were decreased by up to 34% in total for all of the perturbation cases, the remaining 34% laser peak intensity is considerable extent to make use. This good stability of the PCLC laser device is due to the polymerization of the CLC by UV curing. This study will be helpful for practical CLC laser device development.

Solvent-free fluidic organic dye lasers.

We report on the demonstration of liquid organic dye lasers based on 9-(2-ethylhexyl)carbazole (EHCz), so-called liquid carbazole, doped with green- and red-emitting laser dyes. Both waveguide and Fabry-Perot type microcavity fluidic organic dye lasers were prepared by capillary action under solvent-free conditions. Cascade Förster-type energy transfer processes from liquid carbazole to laser dyes were employed to achieve color-variable amplified spontaneous emission and lasing. Overall, this study provides the first step towards the development of solvent-free fluidic organic semiconducting lasers and demonstrates a new kind of optoelectronic applications for liquid organic semiconductors.

Continuous spatial tuning of laser emissions in a full visible spectral range.

In order to achieve a continuous tuning of laser emission, the authors designed and fabricated three types of cholesteric liquid crystal cells with pitch gradient, a wedge cell with positive slope, a wedge cell with negative slope, and a parallel cell. The length of the cholesteric liquid crystal pitch could be elongated up to 10 nm, allowing the lasing behavior of continuous or discontinuous spatial tuning determined by the boundary conditions of the cholesteric liquid crystal cell. In the wedge cell with positive slope, the authors demonstrated a continuous spatial laser tuning in the near full visible spectral range, with a tuning resolution less than 1 nm by pumping with only a single 355 nm laser beam. This continuous tuning behavior is due to the fact that the concentration of pitch gradient matches the fixed helical pitch determined by the cell thickness. This characteristic continuous spatial laser tuning could be confirmed again by pumping with a 532 nm laser beam, over 90 nm in the visible spectral range. The scheme of the spatial laser tuning in the wedge cell bearing a pitch gradient enabled a route to designing small-sized optical devices that allow for a wide tunability of single-mode laser emissions.

Electro-optic Kerr effect in the isotropic phase above the columnar phase of a urea derivative.

The authors have measured the electro-optic Kerr effect in the isotropic phase of a urea derivative. Electric-field-induced birefringence Deltan was observed in the isotropic phase even 30 degrees C above the isotropic-columnar phase transition temperature. The induced birefringence is inversely proportional to temperature, as predicted by the Landau-de Gennes theory. Two distinct regions are identified from the proportionality constants in the isotropic phase; optical second-harmonic generation (SHG) is easily observable in the low-temperature region on applying an electric field, whereas SHG activity does not emerge in the higher-temperature region. The structure of molecular assemblies is discussed based on these experimental results.

Pulse-laser electroholography by use of interference fringe patterns captured by a CCD.

Digital holography is combined with a pulse-laser electroholographic system for a real-time three-dimensional display. Owing to the one-dimensional characteristics of the Bragg-regime acousto-optic spatial-light modulator, vertical parallax cannot be generated from the acoustic signal propagating along the fan-shaped beam direction of the incident laser. To obtain a proper interference pattern, we attach a horizontal slit to the confocal lens system for recording the fringe data, significantly reducing the bandwidth of the vertical fringe data. When the bandwidth-reduced fringe data are displayed by use of a pulse-laser electroholographic system, the clarity and the quality of the image are found to be appreciably improved.