Molecular design of triazine and carbazole based host materials for blue phosphorescent organic emitting diodes.

We synthesized 3-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-methylphenyl)-9-phenyl-9H-carbazole (TrzmPCz) as a new bipolar host material for blue phosphorescent organic light-emitting devices and investigated the electro-optical properties of the blue devices fabricated using the TrzmPCz host. We managed the triplet energy of the host by inserting a methyl substituent in the phenyl linkage between triazine and carbazole. The methyl substituent distorted the backbone structure of TrzmPCz and lead to high triplet energy of 2.79 eV. After optimization of the device structure, the TrzmPCz based organic light-emitting diodes achieved the maximum quantum efficiency of 16.4%, a current efficiency of 32 cd A(-1), and a power efficiency of 21.5 lm W(-1).

Thermal- and photo-induced phase-transition behaviors of a tapered dendritic liquid crystal with photochromic azobenzene mesogens and a bicyclic chiral center.

A ribbon-shaped chiral liquid crystalline (LC) dendrimer with photochromic azobenzene mesogens and an isosorbide chiral center (abbreviated as AZ3 DLC) was successfully synthesized and its major phase transitions were studied by using differential scanning calorimetry (DSC) and linear polarized optical microscopy (POM). Its ordered structures at different temperatures were further identified through structure-sensitive diffraction techniques. Based on the experimental results, it was found that the AZ3 DLC molecule exhibited the low-ordered chiral smectic (Sm*) LC phase with 6.31 nm periodicity at a high-temperature phase region. AZ3 DLC showed the reversible photoisomerization in both organic solvents and nematic (N) LC media. As a chiral-inducing agent, it exhibited a good solubility, a high helical-twisting power, and a large change in the helical-twisting power due to its photochemical isomerization in the commercially available N LC hosts. Therefore, we were able to reversibly "remote-control" the colors in the whole visible region by finely tuning the helical pitch of the spontaneously formed helical superstructures.

A Polyolefin Elastomer Encapsulant Modified by an Ethylene-Propylene-Diene Terpolymer for Photovoltaic Applications.

In this study, a newly designed adhesion promoter, a modified ethylene-propylene-diene terpolymer (m-EPDM), was constructed via a simple thiol-ene click reaction between the ethylene-propylene-diene terpolymer (EPDM) and 3-mercaptopropyltrimethoxysilane (MPTS) to employ polyolefin elastomer (POE) encapsulants in photovoltaic modules. The grafting reaction of MPTS on an EPDM backbone (thiol-ene click reaction) was verified using 1H NMR, 29Si NMR, and SEM/EDX. The thermal and mechanical characteristics of the POE compounds did not significantly change with an increasing m-EPDM content irrespective of the cross-linking state. Interestingly, the adhesion strength to the glass substrate increased linearly with an increasing m-EPDM content until 9 phr. Also, the POE compounds containing more than 12 phr m-EPDM showed cohesion failure of the encapsulant layer, remaining as a residue of the encapsulant layer on the glass surface after peel testing. The damp-heat test was conducted to evaluate the long-term durability of the photovoltaic module encapsulated with m-EPDM, and no significant power loss was found even after 1000 h under the test conditions.

Chemistry of Polythiols and Their Industrial Applications.

Thiols can react with readily available organic substrates under benign conditions, making them suitable for use in chemical, biological, physical, and materials and engineering research areas. In particular, the highly efficient thiol-based click reaction includes the reaction of radicals with electron-rich enes, Michael addition with electron-poor enes, carbonyl addition with isocyanate SN2 ring opening with epoxies, and SN2 nucleophilic substitution with halogens. This mini review provides insights into emerging venues for their industrial applications, especially for the applications of thiol-ene, thiol-isocyanate, and thiol-epoxy reactions, highlighting a brief chemistry of thiols as well as various approaches to polythiol synthesis.

Synthesis and Characterization of Multifunctional Secondary Thiol Hardeners Using 3-Mercaptobutanoic Acid and Their Thiol-Epoxy Curing Behavior.

3-Mercaptobutanoic acid (3-MBA) was synthesized by the less odorous Michael addition pathway using an isothiouronium salt intermediate. Using the synthesized 3-MBA, multifunctional secondary thiol (sec-thiol) compounds were obtained and applied to thiol-epoxy curing systems as hardeners. As the functionality of the sec-thiol hardeners increased, the purity of the product obtained after distillation decreased. The equivalent epoxy mixtures with multifunctional sec-thiol hardeners were evaluated based on their impact on the curing behavior in thiol-epoxy click reactions by differential scanning calorimetry. The thermal features of sec-thiol-epoxy click reactions in the presence of a base catalyst were assessed according to the functionality of the sec-thiol hardeners. Our results showed that sec-thiol hardeners with less reactivity to the epoxy group provide long-term storage stability for the formulated epoxy resin, promising for industrial applications.

Construction, Physical Properties and Foaming Behavior of High-Content Lignin Reinforced Low-Density Polyethylene Biocomposites.

Lignin was chemically modified with oligomeric polyethylene (oPE) to form oPE-grafted lignin (oPE-g-lignin) via lignin surface acylation and a radical coupling reaction with oPE. Then, pristine lignin and oPE-g-lignin were successfully compounded with low-density polyethylene (LDPE) through a typical compounding technique. Due to the oligomeric polyethylene chains grafted to the lignin's surface, the interfacial adhesion between the lignin particles and the LDPE matrix was considerably better in the oPE-g-lignin/LDPE biocomposite than in the pristine-lignin/LDPE one. This demonstrated that oPE-g-lignin can serve as both a biodegradable reinforcing filler, which can be loaded with a higher lignin content at 50 wt-%, and a nucleating agent to increase the crystallization temperature and improve the tensile characteristics of its LDPE biocomposites. Moreover, the foamability of the lignin-reinforced LDPE biocomposites was studied in the presence of a chemical blowing agent (azodicarbonamide) with dicumyl peroxide; for an oPE-g-lignin content up to 20 wt-%, the cell size distribution was quite uniform, and the foam expansion ratios (17.69 ± 0.92) were similar to those of the neat LDPE foam (17.04 ± 0.44).

Construction and Characterization of Polyolefin Elastomer Blends with Chemically Modified Hydrocarbon Resin as a Photovoltaic Module Encapsulant.

In this study, polyolefin elastomer (POE) was blended with a chemically modified hydrocarbon resin (m-HCR), which was modified through a simple radical grafting reaction using γ-methacryloxypropyl trimethoxy silane (MTS) as an adhesion promotor to the glass surface, to design an adhesion-enhanced polyolefin encapsulant material for photovoltaic modules. Its chemical modification was confirmed by 1H and 29Si NMR and FT-IR. Interestingly, the POE blends with the m-HCR showed that the melting peak temperature (Tm) was not changed. However, Tm shifted to lower values with increasing m-HCR content after crosslinking. Additionally, the mechanical properties did not significantly differ with increasing m-HCR content. Meanwhile, with increasing m-HCR content in the POE blend, the peel strength increased linearly without sacrificing their transmittance. The test photovoltaic modules comprising the crosslinked POE blend encapsulants showed little difference in the electrical performance after manufacturing. After 1000 h of damp-heat exposure, no significant power loss was observed.

Optimization of synthetic parameters of high-purity trifunctional mercaptoesters and their curing behavior for the thiol-epoxy click reaction.

The direct esterification reaction between 3-mercaptopropionic acid (3-MPA) and trimethylolpropane (TMP) was conducted in the presence of various catalyst concentrations of p-toluenesulfonic acid (p-TSA) to examine the optimized synthetic conditions needed to produce high-purity trimethylolpropane-tris(3-mercaptopropionate) (TMPMP). The purity of the desired TMPMP and uncompleted side-product reduced as the acid catalyst concentration in this esterification reaction increased while the generation of thioester-based side-product increased. The equivalent ratio between epoxy and the manufactured TMPMP was maintained at 1 : 1 to monitor the curing behavior of the thiol-epoxy click reaction using the DSC technique. The thermal features of the base-catalyzed TMPMP-cured epoxy resin were assessed according to the purity of the TMPMP curing agent.

Preparation of Chemically Modified Lignin-Reinforced PLA Biocomposites and Their 3D Printing Performance.

Using a simple esterification reaction of a hydroxyl group with an anhydride group, pristine lignin was successfully converted to a new lignin (COOH-lignin) modified with a terminal carboxyl group. This chemical modification of pristine lignin was confirmed by the appearance of new absorption bands in the FT-IR spectrum. Then, the pristine lignin and COOH-lignin were successfully incorporated into a poly(lactic acid) (PLA) matrix by a typical melt-mixing process. When applied to the COOH-lignin, interfacial adhesion performance between the lignin filler and PLA matrix was better and stronger than pristine lignin. Based on these results for the COOH-lignin/PLA biocomposites, the cost of printing PLA 3D filaments can be reduced without changing their thermal and mechanical properties. Furthermore, the potential of lignin as a component in PLA biocomposites adequate for 3D printing was demonstrated.

Phase behaviors and structures of a symmetrically tapered biphenylamide.

A symmetrically tapered N,N'-bis[tris[(2-dodecylaminocarbonyl)ethyl]methyl]]-4,4'-biphenylamide (d-C(n)PhA, where n is the number of carbon atoms in the alkyl chains, n = 12), was newly designed and synthesized in order to investigate the supramolecular ordered structures induced by phase separation, hydrogen (H)-bonding, and pi-pi stacking interaction. This symmetrically tapered d-C(12)PhA biphenylamide consists of three different parts: H-bondable hydrophilic amide moieties, a rigid hydrophobic biphenyl aromatic core, and three flexible hydrophobic alkyl chains at each end of the core. Major phase transitions and supramolecular structures in d-C(12)PhA biphenylamide were characterized by differential scanning calorimetry (DSC), one-dimensional (1D) wide-angle X-ray diffraction (WAXD), 1D and 2D Fourier-transform infrared spectroscopy (FT-IR), and solid-state (13)C nuclear magnetic resonance (NMR). The symmetrically tapered d-C(12)PhA biphenylamide formed a hexagonal columnar (Phi(H)) liquid crystalline (LC) mesophase at a cooling process and a highly ordered columnar (Phi(HK)) crystalline phase at a subsequent heating process. Selected area electron diffractions (SAED) from single crystals combined with the results of WAXD and POM suggest that discotic building blocks are constructed by three d-C(12)PhA biphenylamides rotating 60 degrees with respect to neighboring ones and the ABC stacked discotic building blocks further self-assemble into columns and then these columns are laterally close-packed to give nanorods. Furthermore, it was identified that the long axis of column is parallel to the long axis of rods.

5,10,15,20-Tetrakis[4'-(terpyridinyl)phenyl]porphyrin and its RuII complexes: synthesis, photovoltaic properties, and self-assembled morphology.

A novel tetrakis(terpyridinyl)porphyrin derivative and its Ru(II) complexes were efficiently synthesized using microwave enhanced synthesis and shown to possess photovoltaic properties. Transmission electron microscopy and selected area electron diffraction were used to investigate its nanowire self-assembly.

TerpyridineCuII-mediated reversible nanocomposites of single-wall carbon nanotubes: towards metallo-nanoscale architectures.

The self-assembly of Oxi-SWNTs, based on terpyridineCu(II) coordination, produces a thermally stable, neutral [(Oxi-SWNT)(tpyCu(II))m]n nanocomposite possessing notable luminscence properties; quantitative disassembly occurred by treatment with aqueous KCN.

Construction of CdS quantum dots via a regioselective dendritic functionalized cellulose template.

Using regioselective dendritic functionalized cellulose, CdS quantum dot nanoparticles were prepared and their photo-optical properties and morphology as well as the preliminary biocompatibility of the hybrid were investigated.

Highly efficient and color tunable thermally activated delayed fluorescent emitters using a "twin emitter" molecular design.

High efficiency and color tuning of thermally activated delayed fluorescent emitters were achieved at the same time by designing emitters with a twin emitter molecular design. The control of the interconnect position between two emitters could manage the emission spectrum of the thermally activated delayed fluorescent emitters without affecting the quantum efficiency.

Construction of triangular metallomacrocycles: [M3(1,2-bis(2,2':6',2''-terpyridin-4-yl-ethynyl)benzene)3][M = Ru(II), Fe(II), 2Ru(II)Fe(II)].

Complexation of a predesigned (1,2-bis(2,2':6',2''-terpyridin-4-yl-ethynyl)benzene) ligand possessing a 60 degrees angle between two terpyridines with transition metals [Fe(II) and Ru(II)] afforded the self-assembled, triangular metallomacrocycles.

Design, self-assembly, and photophysical properties of pentameric metallomacrocycles: [M5(N-hexyl[1,2-bis(2,2':6',2''-terpyridin-4-yl)]carbazole)5][M = Fe(II), Ru(II), and Zn(II)].

A novel family of metallopentacycles was constructed by the facile self-assembly of a bis(terpyridine)-carbazole monomer utilizing terpyridine-metal(II)-terpyridine connectivity; its photophysical properties were investigated.

Stable blue thermally activated delayed fluorescent organic light-emitting diodes with three times longer lifetime than phosphorescent organic light-emitting diodes.

High quantum efficiency above 18% and extended lifetime three times longer than that of phosphorescent organic light-emitting diodes (OLEDs) are demonstrated in blue thermally activated delayed fluorescent OLEDs.

Synthesis of dibenzothiophene-based host materials with a dimesitylborane substituent and their green PHOLED performances.

In the two isomeric dibenzothiophene-based host materials, the different linkages between dibenzothiophene and dimesitylborane on a phenyl spacer dictated their photophysical properties. The performances of Ir(ppy)2(acac)-based green phosphorescent devices with two isomeric host materials were similar regardless of different linkage positions.

Benzofurocarbazole and benzothienocarbazole as donors for improved quantum efficiency in blue thermally activated delayed fluorescent devices.

Benzofurocarbazole and benzothienocarbazole were used as electron donors of thermally activated delayed fluorescence (TADF) emitters and the performances of the TADF devices were examined. The benzofurocarbazole and benzothienocarbazole donor moieties were better than carbazole as the electron donors of the TADF emitters.

Rational design of host materials for phosphorescent organic light-emitting diodes by modifying the 1-position of carbazole.

A novel carbazole moiety with bromine at the 1-position of carbazole was synthesized and four carbazole compounds derived from the 1-position modified carbazole were developed as the host materials for phosphorescent organic light-emitting diodes. The 1-position modified carbazole was coupled with another carbazole to prepare bicarbazole intermediates, which were substituted with 4,6-diphenyltriazine to yield four bicarbazole derivatives modified with the electron deficient diphenyltriazine unit. The triplet host materials showed high quantum efficiency above 20% and low driving voltage below 5.0 V at 1000 cd m(-2) in green phosphorescent organic light-emitting diodes.