Red-Colored Circularly Polarized Luminescence from a Benzo-Fused BODIPY-BINOL Complex.

Red emission with sharp bandwidth and high quantum yield is a desired characteristic for organic chromophores in optoelectronic, spintronic, and biomedical applications. Here, we observe circularly polarized luminescence (CPL) with these characteristics from a benzo-fused BODIPY-BINOL complex (1). Using time-resolved optical spectroscopy, electrochemistry, and density functional theory calculations, we showed that the emissive excited state of 1 does not have a charge-transfer (CT) character, unlike that of the regular BODIPY counterpart (2). The rigidity and the lack of CT character make this class of molecules an appealing platform for CPL-active molecules in the red spectral region, with ample room for improvement in the dissymmetry factor and brightness.

Chiral H-aggregation-induced large stokes shift with CPL generation assisted by α-helical poly(L-lysine) substructure.

Fluorescent materials with large Stokes shifts have significant potential for use in optical applications. Typically, a synthetic design strategy is utilized for this purpose. In this study, we demonstrated a novel method by binding a chiral template to a nonchiral fluorescent agent without chemical modification. Specifically, α-helical poly(L-lysine) was employed as the chiral template, which interacted with a disulfonic fluorescent dye, such as NK2751. The dye caused excimer luminescence by inducing the formation of a chirally H-aggregated dimer only when poly(L-lysine) was in an α-helical shape. The result was a Stokes shift of 230 nm. Similar effects were not observed when the chiral template was in a random coil condition and the Stokes shift was less than 40 nm. These findings imply that H-aggregated dimerization, which often results in quenching, permits the electronic transitions necessary for fluorescence events by the formation of the chirally twisted state. In addition, we introduce for the first time the generation of circularly polarized luminescence using the chirality induction phenomena in a dye supported by poly(L-lysine).

Zwitterionic polymer-terminated porous silica stationary phases for highly selective separation in hydrophilic interaction chromatography.

We described two novel zwitterionic polymer-terminated porous silica stationary phases containing the same pyridinium cation and anions of different side chains (carboxylate and phosphonate groups) for use in hydrophilic interaction liquid chromatography (HILIC). These two novel columns were prepared by polymerizing 4-vinylpyridine and grafting it onto a silica surface, followed by quaternization reaction with 3-bromopropionic acid (Sil-VPC24) and (3-bromopropyl) phosphonic acid (Sil-VPP24), which possess positively charged pyridinium groups, and negatively charged carboxylate and phosphonate groups, respectively. The products obtained were verified through relevant characterization techniques such as elemental analysis, Fourier-transform infrared spectroscopy, thermogravimetric analysis, Zeta potential analysis, and Brunauer-Emmett-Teller analysis. The retention properties and mechanisms of different types of compounds (neutral, cationic, and anionic) on the two zwitterionic-modified silica stationary phases were studied by varying the buffer salt concentration and pH of the eluent. The separation of phenol and aromatic acids, disubstituted benzene isomers, sulfonamide drugs, as well as nucleosides/nucleobases were investigated on the two packed novel columns and a commercial zwitterionic column in identical HILIC mode, ensuring a thorough comparison between both novel columns and with a commercial standard. The results illustrated that various compounds could be separated up to various efficiencies based on the mechanism of hydrophilic interaction-based retention between the solutes and the two zwitterionic polymer stationary phases. The Sil-VPP24 column demonstrated the best separation performance out of the three, as well as flexible selectivity and excellent resolution. Both novel columns exhibited excellent stability and chromatographic repeatability for the separation of seven nucleosides and bases.

Chemical redox-induced chiroptical switching of supramolecular assemblies of viologens.

A chiral supramolecular assembly exhibiting redox-induced changes in its chiroptical properties was prepared using viologen-modified glutamide (G-V2+) derivatives. Achiral viologen moieties in the G-V2+ assembly were chirally orientated by glutamide groups, affording a unique orange-colored solution, with a visible absorption band at around 470 nm, having electronic circular dichroism (CD) signals (molar ellipticity [θ] = 0.58 × 105 deg cm2 dmol-1: absorption dissymmetry factors (g) = 5.2 × 10-3 at 512 nm). The G-V2+ could be reduced to its cation radical (G-V+˙) but retains its chiral assembly. After chemical reduction, the color change from orange to blueish violet, indicating an absorption band at approximately 560 nm, and the sign change of the CD signal from positive to negative ([θ] = -0.36 × 105 deg cm2 dmol-1; g = -2.9 × 10-3 at 580 nm) were observed in water. Subsequent oxidation re-introduces the G-V2+ chiroptical behavior before reduction.

A Molecular Shape Recognitive HPLC Stationary Phase Based on a Highly Ordered Amphiphilic Glutamide Molecular Gel.

Chiral glutamide-derived lipids form self-assembled fibrous molecular gels that can be used as HPLC organic phases. In this study, HPLC separation efficiency was improved through the addition of branched amphiphilic glutamide lipids to the side chains of a terminally immobilized flexible polymer backbone. Poly(4-vinylpyridine) with a trimethoxysilyl group at one end was grafted onto the surface of porous silica particles (Sil-VP15, polymerization degree = 15), and the pyridyl side chains were quaternized with a glutamide lipid having a bromide group (BrG). Elemental analysis indicated that the total amount of the organic phase of the prepared stationary phase (Sil-VPG15) was 38.0 wt%, and the quaternization degree of the pyridyl groups was determined to be 32.5%. Differential scanning calorimetric analysis of a methanol suspension of Sil-VPG15 indicated that the G moieties formed a highly ordered structure below the phase transition temperature even on the silica surface, and the ordered G moieties exhibited a gel-to-liquid crystalline phase transition. Compared with a commercially available octadecylated silica column, the Sil-VPG15 stationary phase showed high selectivity toward polycyclic aromatic hydrocarbons, and particularly excellent separations were obtained for geometrical and positional isomers. Sil-VPG15 also showed highly selective separation for phenol derivatives, and bio-related molecules containing phenolic groups such as steroids were successfully separated. These separation abilities are probably due to multiple interactions between the elutes and the highly ordered functional groups, such as the pyridinium and amide groups, on the highly ordered molecular gel having self-assembling G moieties.

Enantioselective Self-Assembled Nanofibrillar Network with Glutamide-Based Organogelator.

A chiral molecular gelation system, as a chiral host, was used to effectively realize enantioselectivity using the simple carboxylic acid functional group. For this purpose, an L-glutamic-acid-based lipidic amphiphile (G-CA) with a carboxylic head group was selected and its responsiveness to cationic guest molecules was investigated. The dispersion morphology of G-CA in its solution state was examined by confocal and transmission electron microscopies, while interactions between the G-CA, as the host system, and guest molecules were evaluated by UV-visible, circular dichroism, and fluorescence spectroscopies. As a result, enantioselectivity was effectively induced when G-CA formed highly ordered aggregates that provide negatively charged surfaces in which carboxyl groups are assembled in highly ordered states, and when the two cationic groups of the guest molecule are attached to this surface through multiple interactions.

Lanthanide ion-doped silica nanohelix: a helical inorganic network acts as a chiral source for metal ions.

We demonstrate that lanthanide ions doped in nanometrical silica helices with a chirally arranged siloxane network without any organic mediates show induced chiroptical properties such as circular dichroism and circularly polarized luminescence.

Structural and Electronic Influences on Rates of Tertpyridine-Amine CoIII -H Formation During Catalytic H2 Evolution in an Aqueous Environment.

In this work, the differences in catalytic performance for a series of Co hydrogen evolution catalysts with different pentadentate polypyridyl ligands (L), have been rationalized by examining elementary steps of the catalytic cycle using a combination of electrochemical and transient pulse radiolysis (PR) studies in aqueous solution. Solvolysis of the [CoII -Cl]+ species results in the formation of [CoII (κ4 -L)(OH2 )]2+ . Further reduction produces [CoI (κ4 -L)(OH2 )]+ , which undergoes a rate-limiting structural rearrangement to [CoI (κ5 -L)]+ before being protonated to form [CoIII -H]2+ . The rate of [CoIII -H]2+ formation is similar for all complexes in the series. Using E1/2 values of various Co species and pKa values of [CoIII -H]2+ estimated from PR experiments, we found that while the protonation of [CoIII -H]2+ is unfavorable, [CoII -H]+ reacts with protons to produce H2 . The catalytic activity for H2 evolution tracks the hydricity of the [CoII -H]+ intermediate.

Fabrication of Carbon-Like, π-Conjugated Organic Layer on a Nano-Porous Silica Surface.

This paper presents a new type of black organic material-porous silica composite providing an extremely highly selective adsorption surface. This black composite was prepared by lamination on nano-sized pores with a carbon-like, π-extended structure, which can be converted via the on-site polymerization of 1,5-dihydroxynaphthalene with a triazinane derivative and a thermally induced condensation reaction with denitrification. This bottom-up fabrication method on porous materials had the great advantage of maintaining the pore characteristics of a raw porous material, but also the resultant black surface exhibited an extremely high molecular-shape selectivity; for example, that for trans- and cis-stilbenes reached 14.0 with the black layer-laminated porous silica, whereas it was below 1.2 with simple hydrophobized silica.

Extreme enhancement of secondary chirality through coordination-driven steric changes of terpyridyl ligand in glutamide-based molecular gels.

Aggregation-induced chirality is potentially useful in sensor technology applications. Herein we show extreme enhancement of secondary chirality through coordination-driven steric changes of terpyridyl ligand in molecular gels. The secondary chirality reflecting on enhancement of chiral signals (i.e., circular dichroism (CD) and circularly polarised luminescence (CPL)) of the molecular gels formed from glutamide-attached terpyridine (G-tpy) is extremely enhanced by the coordination of its terpyridyl groups to metal ions such as Cu2+, Zn2+ and Ru2+, which is due to dramatic changes in the stacked structure of the chromophore groups through the formation of metal ion complex. Metal-free terpyridine exists in a non-planar geometry, which suppress π-π stacking interactions among aggregates. The planarity of the terpyridyl group is improved through metal-ion complexation, which induces the metal-ion-coordinated terpyridyl groups to stack. The thermal stabilities of the CD signals are strongly affected by the metal-ion species. CPL signal is generated in the molecular gel formed from G-tpy-Zn2+ complex accompanied by chelation-enhanced fluorescence. It is expected that large and sensitive coordination-driven secondary chirality signals (CD and CPL) are useful for sensing guest molecules and the surrounding environment.

Emission-Color Control in Polymer Films by Memorized Fluorescence Solvatochromism in a New Class of Totally Organic Fluorescent Nanogel Particles.

In this work, a new class of totally organic fluorescent nanogel particles and their exceptionally specific behaviors based on their unique structures are introduced, which draws a sharp line from conventional fluorophore-doped and fluorophore-branched-type particles. The nanogel particles, the diameter of which could be controlled by adjusting reaction conditions, such as the solvent system, were spontaneously fabricated with a spherical shape by direct polymerization of non-heterocyclic aromatic compounds, such as 2,6-dihydroxyanthracene, 2,6-dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene with triazinane as the cross-linker. A fluorophoric moiety formed from a polymer main chain was realized in the particle, and consequently, the resultant content of the fluorophoric moiety was around 70-80 wt % per particle. The uniqueness and versatility of the particles can be emphasized by their good compatibility with various solvents due to their amphiphilic and ampholytic swelling properties, but also by their remarkable fluorescent solvatochromism in the dispersion state. Furthermore, these behaviors were preserved even in their polymer composite system. This study also demonstrates that various fluorescent polymer films can be fabricated with emission color control due to memorization of the solvatochromism phenomenon of the dispersed fluorescent nanoparticles.

Preparation of High Refractive Index Composite Films Based on Titanium Oxide Nanoparticles Hybridized Hydrophilic Polymers.

Optical materials with high refractive index (n) have been rapidly improved because of urgent demands imposed by the development of advanced photonic and electronic devices such as solar cells, light emitting diodes (LED and Organic LED), optical lenses and filters, anti-reflection films, and optical adhesives. One successful method to obtain high refractive index materials is the blending of metal oxide nanoparticles such as TiO2 and ZrO2 with high n values of 2.1-2.7 into conventional polymers. However, these nanoparticles have a tendency to agglomerate by themselves in a conventional polymer matrix, due to the strong attractive forces between them. Therefore, there is a limitation in the blending amount of inorganic nanoparticles. In this paper, various hydrophilic polymers such as poly(N-hydroxyl acrylamide) (pHEAAm), poly(vinyl alcohol), poly(ethylene glycol), and poly(acrylic acid) were examined for preparation of high refractive index film based on titanium oxide nanoparticle (TiNP) dispersed polymer composite. The hydrogen bonding sites in these hydrophilic polymers would improve the dispersibility of inorganic nanoparticles in the polymer matrix. As a result, pHEAAm exhibited higher compatibility with titanium oxide nanoparticles (TiNPs) than other water-soluble polymers. Transparent hybrid films were prepared by mixing pHEAAm with TiNPs and drop casting the mixture onto a glass plate. The refractive indices of the films were in good agreement with calculated values. The compatibility of TiNPs with pHEAAm was dependent on the surface characteristics of TiNPs. TiNPs with the highest observed compatibility could be hybridized with pHEAAm at concentrations of up to 90 wt%, and the refractive index of the corresponding film reached 1.90. The high compatibility of TiNPs with pHEAAm may be related to the hydrophilicity and amide and hydroxyl moieties of pHEAAm, which cause hydrogen bond formation on the TiO2 surface. The obtained thin film was slightly yellow due to the color of the original TiNP dispersion; however, the transmittance of the film was higher than 80% in the wavelength range from 480 to 900 nm.

A room-temperature phosphorescent polymer film containing a molecular web based on one-dimensional chiral stacking of a simple luminophore.

We propose a new approach for a totally organic, room-temperature phosphorescent system with a lifetime on the order of milliseconds, which is achieved by promotion of the one-dimensional chiral stacking of a simple, small fluorophore in a solution state. The versatility of this system is highlighted by its good applicability to the fabrication of a phosphorescent polymer film. This paper demonstrates the first example of a room-temperature phosphorescent polymer film prepared with our methodology.

Induction of Strong and Tunable Circularly Polarized Luminescence of Nonchiral, Nonmetal, Low-Molecular-Weight Fluorophores Using Chiral Nanotemplates.

A new strategy is described for generating strong circularly polarized luminescence with highly tunable emission bands through chiral induction in nonchiral, totally organic, low-molecular-weight fluorescent dyes by chiral nanotemplate systems. Our approach allows the first systematic investigation to clarify the correlation between the circular dichroism and circularly polarized luminescence intensities. As a result, a dilute solution system with the highest circularly polarized luminescence intensity achieved to date and a dissymmetry factor of over 0.1 was identified.

A remarkable enhancement of selectivity towards versatile analytes by a strategically integrated H-bonding site containing phase.

A double ß-alanylated L-glutamide-derived organic phase has been newly designed and synthesized in such a way that integrated H-bonding (interaction) sites make it very suitable for the separation of versatile analytes, including shape-constrained isomers, and nonpolar, polar and basic compounds. The ß-alanine residues introduced into two long-chain alkyl group moieties provide ordered polar groups through H-bonding among the amide groups.

Design of C18 Organic Phases with Multiple Embedded Polar Groups for Ultraversatile Applications with Ultrahigh Selectivity.

For the first time, we synthesized multiple embedded polar groups (EPGs) containing linear C18 organic phases. The new materials were characterized by elemental analysis, IR spectroscopy, (1)H NMR, diffuse reflectance infrared Fourier transform (DRIFT), solid-state (13)C cross-polarization magic angle spinning (CP/MAS) NMR, suspended-state (1)H NMR, and differential scanning calorimetry (DSC). (29)Si CP/MAS NMR was carried out to investigate the degree of cross-linking of the silane and silane functionality of the modified silica. Solid-state (13)C CP/MAS NMR and suspended-state (1)H NMR spectroscopy indicated a higher alkyl chain order for the phase containing four EPGs than for the phase with three EPGs. To correlate the NMR results with temperature-dependent chromatographic studies, standard reference materials (SRM 869b and SRM 1647e), a column selectivity test mixture for liquid chromatography was employed. A single EPG containing the C18 phase was also prepared in a similar manner to be used as a reference column especially for the separation of basic and polar compounds in reversed-phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC), respectively. Detailed chromatographic characterization of the new phases was performed in terms of their surface coverage, hydrophobic selectivity, shape selectivity, hydrogen bonding capacity, and ion-exchange capacity at pH 2.7 and 7.6 for RPLC as well as their hydrophilicity, the selectivity for hydrophilic-hydrophobic substituents, the selectivity for the region and configurational differences in hydrophilic substituents, the evaluation of electrostatic interactions, and the evaluation of the acidic-basic nature for HILIC-mode separation. Furthermore, peak shapes for the basic analytes propranolol and amitriptyline were studied as a function of the number of EPGs on the C18 phases in the RPLC. The chromatographic performance of multiple EPGs containing C18 HILIC phases is illustrated by the separation of sulfa drugs, ß-blockers, xanthines, nucleic acid bases, nucleosides, and water-soluble vitamins. Both of the phases showed the best performance for the separation of shape-constrained isomers, nonpolar, polar, and basic compounds in RPLC- and HILIC-mode separation of sulfa drugs, and other polar and basic analytes compared to the conventional alkyl phases with and without embedded polar groups and HILIC phases. Surprisingly, one phase would be able to serve the performance of three different types of phases with very high selectivity, and we named this phase the "smart phase". Versatile applications with a single column will reduce the column purchasing cost for the analyst as well as achieve high separation, which is challenging with the commercially available columns.

Electrocatalytic CO2 Reduction with a Homogeneous Catalyst in Ionic Liquid: High Catalytic Activity at Low Overpotential.

We describe a new strategy for enhancing the efficiency of electrocatalytic CO2 reduction with a homogeneous catalyst, using a room-temperature ionic liquid as both the solvent and electrolyte. The electrochemical behavior of fac-ReCl(2,2'-bipyridine)(CO)3 in neat 1-ethyl-3-methylimidazolium tetracyanoborate ([emim][TCB]) was compared with that in acetonitrile containing 0.1 M [Bu4N][PF6]. Two separate one-electron reductions occur in acetonitrile (-1.74 and -2.11 V vs Fc(+/0)), with a modest catalytic current appearing at the second reduction wave under CO2. However, in [emim][TCB], a two-electron reduction wave appears at -1.66 V, resulting in a ∼0.45 V lower overpotential for catalytic reduction of CO2 to CO. Furthermore, the apparent CO2 reduction rate constant, kapp, in [emim][TCB] exceeds that in acetonitrile by over one order of magnitude (kapp = 4000 vs 100 M(-1) s(-1)) at 25 ± 3 °C. Supported by time-resolved infrared measurements, a mechanism is proposed in which an interaction between [emim](+) and the two-electron reduced catalyst results in rapid dissociation of chloride and a decrease in the activation energy for CO2 reduction.

Manipulation and assembly of small objects in liquid crystals by dynamical disorganizing effect of push-pull-azobenzene-dye.

The phase transition of a nematic liquid crystal containing a push-pull azobenzene dye could be induced efficiently during irradiation with visible light. The dynamical disorganizing effect of the push-pull azobenzene dye on the liquid crystalline order through its trans-cis-trans photoisomerizaion cycle under visible light was contributed to the efficient phase transition. Then, the effects of light irradiation on the motion of small objects dispersed in the liquid crystals containing the push-pull azobenzene were explored, and the manipulation and assembly of those objects were successfully achieved in the nematic phase but also in the smectic phase. The combination of the photo-controlled dynamical change in the liquid crystalline order and the intrinsic self-assembly property of a liquid crystal is promising for use in technologies that require not only the organization of small objects but also the photo-driving of nano- and micro-sized mechanical materials.

Modulation of polymer refractive indices with diamond nanoparticles for metal-free multilayer film mirrors.

Modulation of the refractive index of a polymer was achieved by combining it with diamond nanoparticles (NDs). The increase in the refractive index was controlled by the amount of NDs added, according to the Lorentz-Lorenz equation. The refractive index of poly(vinyl alcohol) (PVA), which was used as the base polymer, increased from 1.52 to 1.88. A multilayer film consisting of alternating layers of ND-PVA composite and poly(methyl methacrylate) exhibited ca. 80% reflectance with 10 bilayers.

Thermal and Photochemical Control of Molecular Orientation of Azo-Functionalized Polymer Liquid Crystals and Application for Photo-Rewritable Paper.

A photo-responsive multi-bilayered film consisting of azobenzene polymer liquid crystals (PA6Az1) and poly(vinyl alcohol) (PVA) has been prepared on a glass substrate by alternate spin coating of the polymer solutions. The reflectivity of the multi-bilayered film disappears by annealing at 80 °C. The disappearance of the reflection by the annealing is related to the thermal out-of-plane molecular orientation of PA6Az1 even in the multi-bilayered film, which leads to a very small difference in refractive indices between PA6Az1 and PVA. The reflectance of the multi-bilayered film is increased again by UV irradiation because of the transformation from the out-of-plane orientation to an in-plane random orientation. In this way, on-off switching of the reflection is achieved by combination of the thermally spontaneous out-of-plane molecular orientation and following photoisomerization of PA6Az1 comprising the multi-bilayered film.