Small Molecule Host Research Articles

Increased Electromer Formation and Charge Trapping in Solution-Processed versus Vacuum-Deposited Small Molecule Host Materials of Organic Light-Emitting Devices

We investigate and compare between organic light-emitting devices (OLEDs) fabricated by solution-coating versus vacuum-deposition. Electroluminescence, photoluminescence, and chromatographic measurements on typical OLED host materials reveal significant electromer formation in layers fabricated by solution-processing, pointing to stronger intermolecular interactions in these systems. Delayed electroluminescence measurements reveal that solution-processed layers also have increased charge traps. The findings provide insights on the morphological differences between solution-processed and vacuum-deposited materials and shed light on the root causes behind the lower electroluminescence stability of solution-processed OLEDs.

Potent in vitro and in vivo antifungal activity of a small molecule host defense peptide mimic through a membrane-active mechanism

Lethal systemic fungal infections of Candida species are increasingly common, especially in immune compromised patients. By in vitro screening of small molecule mimics of naturally occurring host defense peptides (HDP), we have identified several active antifungal molecules, which also exhibited potent activity in two mouse models of oral candidiasis. Here we show that one such compound, C4, exhibits a mechanism of action that is similar to the parent HDP upon which it was designed. Specifically, its initial interaction with the anionic microbial membrane is electrostatic, as its fungicidal activity is inhibited by cations. We observed rapid membrane permeabilization to propidium iodide and ATP efflux in response to C4. Unlike the antifungal peptide histatin 5, it did not require energy-dependent transport across the membrane. Rapid membrane disruption was observed by both fluorescence and electron microscopy. The compound was highly active in vitro against numerous fluconazole-resistant clinical isolates of C. albicans and non-albicans species, and it exhibited potent, dose-dependent activity in a mouse model of invasive candidiasis, reducing kidney burden by three logs after 24 hours, and preventing mortality for up to 17 days. Together the results support the development of this class of antifungal drug to treat invasive candidiasis.

Green phosphorescent organic light-emitting devices based on different electron transport layers combining with fluorescent sub-monolayer

We report a small molecule host of 4,4(-N,N)-dicarbazole-biphenyl (CBP) doped with 8% tris(2-phenylpyridine) iridium (Irppy3) for use in efficient green phosphorescent organic light-emitting devices (PHOLEDs) combined with different electron transport layers of Alq and BAlq. The PHOLEDs exhibit maximum current efficiency and power efficiency of 19.8 cd/A and 6.21 lm/W, respectively. The high performance of such PHOLEDs is attributed to the better electron mobile ability of BAlq and sub-monolayer quinacridone (QAD) as carrier trapping layer and equal charge carrier mobilities of hole and electron to form the broad carrier recombination zone in the emitting layer, which can reduce the triplet-triplet annihilation and improve the efficiency of the device.

Slot Die Coated and Flexo Printed Highly Efficient SMOLEDs

A basic solution‐processable organic light‐emitting diode (OLED) stack comprising two organic layers is presented in this study. The hole injection layer (poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate), PEDOT:PSS) is slot die coated and flexographically printed for process comparison in terms of film homogeneity and the device performance. The emissive layer consisting of a small molecule host–guest system with a green triplet emitter is slot die coated. The single layer thicknesses are mapped by an in‐house developed imaging color reflectometry enabling the precise measurement of the layer thicknesses over the whole coating area (>50 cm2). Luminance, current density, and light and current efficiency are defined for two different pixel sizes with the active area of 6 × 4 and 14 × 14 mm2. A total of 100 OLEDs are measured showing a very low standard deviation for the different pixels. The solely slot die coated OLEDs show much higher current and power efficiency than the OLEDs with flexographically printed PEDOT:PSS. Small molecule OLEDs reach efficiencies up to 30 cd A−1 and 8 lm W−1. Additionally OLED demonstrators with an active area of ≈27 cm2 are fabricated.

An Expanded Palette of Xenon-129 NMR Biosensors

ConspectusMolecular imaging holds considerable promise for elucidating biological processes in normal physiology as well as disease states, by determining the location and relative concentration of specific molecules of interest. Proton-based magnetic resonance imaging (1H MRI) is nonionizing and provides good spatial resolution for clinical imaging but lacks sensitivity for imaging low-abundance (i.e., submicromolar) molecular markers of disease or environments with low proton densities. To address these limitations, hyperpolarized (hp) 129Xe NMR spectroscopy and MRI have emerged as attractive complementary methodologies. Hyperpolarized xenon is nontoxic and can be readily delivered to patients via inhalation or injection, and improved xenon hyperpolarization technology makes it feasible to image the lungs and brain for clinical applications.In order to target hp 129Xe to biomolecular targets of interest, the concept of “xenon biosensing” was first proposed by a Berkeley team in 2001. The development of xenon biosensors has since focused on modifying organic host molecules (e.g., cryptophanes) via diverse conjugation chemistries and has brought about numerous sensing applications including the detection of peptides, proteins, oligonucleotides, metal ions, chemical modifications, and enzyme activity. Moreover, the large (∼300 ppm) chemical shift window for hp 129Xe bound to host molecules in water makes possible the simultaneous identification of multiple species in solution, that is, multiplexing. Beyond hyperpolarization, a 106-fold signal enhancement can be achieved through a technique known as hyperpolarized 129Xe chemical exchange saturation transfer (hyper-CEST), which shows great potential to meet the sensitivity requirement in many applications.This Account highlights an expanded palette of hyper-CEST biosensors, which now includes cryptophane and cucurbit[6]uril (CB[6]) small-molecule hosts, as well as genetically encoded gas vesicles and single proteins. In 2015, we reported picomolar detection of commercially available CB[6] via hyper-CEST. Inspired by the versatile host–guest chemistry of CB[6], our lab and others developed “turn-on” strategies for CB[6]-hyper-CEST biosensing, demonstrating detection of protein analytes in complex media and specific chemical events. CB[6] is starting to be employed for in vivo imaging applications. We also recently determined that TEM-1 β-lactamase can function as a single-protein reporter for hyper-CEST and observed useful saturation contrast for β-lactamase expressed in bacterial and mammalian cells. These newly developed small-molecule and genetically encoded xenon biosensors offer significant potential to extend the scope of hp 129Xe toward molecular MRI.

Sustained release profile of quatro stimuli nanocontainers as a multi sensitive vehicle exploiting cancer characteristics

A versatile drug delivery carrier that responds to external stimuli was synthesized via the emulsion polymerization process. This simple two-step process was carried out by using Poly (Methyl Methacrylate) as a soft template and a series of monomers, with desired properties, as coating monomers. It is noteworthy that during shell fabrication (2nd step) an inner cavity is created inside the nanocontainers that can be used as a host for small drug molecules. The thermo-, pH- and redox sensitive monomers used in the coating procedure were Dimethyl Amino Ethyl Methacrylate (DMAEMA), Acrylic Acid (AA) and N,N′-(disulfanediylbis(ethane-2,1-diyl))bis(2-methylacrylamide) (Disulfide or DS), respectively. It has to be noted that DMAEMA is also pH- sensitive and acts synergistically with AA. The surface of the multi-stimuli nanocontainers was functionalized with magnetite nanoparticles in order to induce an alternating magnetic field (AMF) sensitivity. By using AMF in various strenghts and frequencies, the temperature of the final multi-stimuli nanocontainers (Q-NCs) can be increased in a controlled manner resulting in the Hyperthermia phenomenon. Loading and release studies were carried out using the anthracycline drug, Doxorubicin, aiming at the confirmation of the release mechanism.

Dimensionality Alteration and Intra- versus Inter-SBU Void Encapsulation in Zinc Phosphate Frameworks.

4,4'-Bipyridine-N-oxide (BIPYMO, 1), a less commonly employed coordination polymer linker, has been used as a ditopic spacer to bridge double-four-ring (D4R) zinc phosphate clusters to form novel framework coordination polymers. Zinc phosphate framework compounds [Zn4(X-dipp)4(BIPYMO)2]n·2MeOH [X = H (2), Cl (3), Br (4), I (5); dipp = 2,6-diisopropylphenyl phosphate] have been obtained by treating a methanol solution of zinc acetate with X-dippH2 and BIPYMO (in a 1:1:1 molar ratio) at ambient conditions. Framework phosphates 2-5 can also be obtained by treating the preformed D4R cubanes [Zn(X-dipp)(DMSO)]4 with required quantities of BIPYMO in methanol. Single-crystal X-ray diffraction studies reveal that these framework solids are two-dimensional (2D) networks as opposed to the diamondoid networks obtained when the parent unoxidized 4,4'-bipyridine is used as the linker (Inorg. Chem. 2014, 53, 8959). The two types of voids (viz., smaller intra-D4R and larger inter-D4R) present in these framework solids can be utilized for different types of encapsulation processes. For example, the in situ generated 2D framework 2 encapsulates fluoride ions accompanied by a change in the dimensionality of the framework to yield {[(nC4H9)4N][F@(Zn4(dipp)4(BIPYMO)2)]}n (6). The three-dimensional framework 6 represents the first structurally characterized example of a fluoride-ion-encapsulated polymeric coordination compound or a metal-organic framework. The possibility of utilizing inter-D4R voids as hosts for small organic molecules has been explored by treating in situ generated 2 with a series of organic molecules of appropriate size. Framework 2 has been found to be a selective host for benzil and not for other structurally similar molecules such as benzoquinone, benzidine, anthracene, naphthalene, α-pyridoin, etc. The benzil-occluded isolated framework [benzil@{Zn4(dipp)4(BIPYMO)2}]n (7) has been isolated as single crystals, and its crystal structure determination revealed the binding of benzil molecules to the framework through strong π-π interactions.

A Rhizobium radiobacter Histidine Kinase Can Employ Both Boolean AND and OR Logic Gates to Initiate Pathogenesis.

The molecular logic gates that regulate gene circuits are necessarily intricate and highly regulated, particularly in the critical commitments necessary for pathogenesis. We now report simple AND and OR logic gates to be accessible within a single protein receptor. Pathogenesis by the bacterium Rhizobium radiobacter is mediated by a single histidine kinase, VirA, which processes multiple small molecule host signals (phenol and sugar). Mutagenesis analyses converged on a single signal integration node, and finer functional analyses revealed that a single residue could switch VirA from a functional AND logic gate to an OR gate where each of two signals activate independently. Host range preferences among natural strains of R. radiobacter correlate with these gate logic strategies. Although the precise mechanism for the signal integration node requires further analyses, long-range signal transmission through this histidine kinase can now be exploited for synthetic signaling circuits.

Phosphorescent hybrid organic-inorganic light emitting devices with solution-processed small molecule emissive layers

We report efficient phosphorescent hybrid organic-inorganic light emitting devices using poly(ethylenimine) as electron-injection layer and interfacial modifier for metal oxides and solution-processed small molecule emissive layers. As a first step, the hole transport layers with various HOMO levels and the hole mobility values including TAPC, TCTA and mCP are evaluated. The results indicate that devices using a TAPC layer show the best luminance and power efficiencies. Subsequently, the optimum phosphor concentration is determined to be ca. 5%. Enlarged efficiency roll-off with increasing current density is observed in devices using the phosphor concentration above the optimum value. We also investigate the morphologies of films having different phosphor concentrations on the top of bare or PEIE-covered glass substrates, which is closely related to device performance. All the films have the RMS values of ca. 1 nm, indicating high-quality solution processed small molecule films. The blue, yellow and red devices show the maximum external quantum efficiencies of 17.3%, 10.7% and 7.3%, respectively. These efficiencies are 17.0%, 10.6% and 5.8% at 1000 cd·m-2, only showing a small roll-off, which can be attributed to alleviated triplet-triplet and triplet-polaron interactions in a broad carrier recombination zone due to using the mixed hole-transport and electron-transport materials as the co-hosts. In addition, these devices exhibit the respective Commission International Eclairage (CIE) coordinates of (0.16, 0.36), (0.50, 0.49) and (0.66, 0.32), which almost traverse the whole visible light region. Furthermore, the hybrid two-colored white devices show a luminance efficiency of 31 cd·A-1, power efficiency of 14.8 lm·W-1 at 1000 cd·m-2 and the operating current-insensitive CIE coordinates of (0.32, 0.42). The efficiencies represent the significant improvement over the previously reported values, which can be attributed to high-quality small molecule films on PEIE, and in particular to the unique properties of small molecule host materials such as balanced carrier transport and high triplet energy. Further efforts including selection of high-mobility electron transport host material and phosphors with high luminescence quantum yield are made to increase the efficiency and reliability of hybrid organic-inorganic light emitting device.

High morphology stability and ambipolar transporting host for use in blue phosphorescent single-layer organic light-emitting diodes

The authors report a small molecule host of 2,7-bis(diphenylphosphoryl)-9-[4-(N,N-diphenylamino)phenyl]-9-phenylfluorene (POAPF) doped with 8wt% iridium(III)-bis[(4,6-difluorophenyl)pyridinato-N,C2′]picolinate (FIrpic) for use in efficient and single-layer blue phosphorescent organic light-emitting diodes (PHOLEDs) exhibiting a maximum external quantum efficiency of ∼20.3% at brightness of 100cd/m2. The high performance of such single layer PHOLEDs is attributed to the POAPF host’s high morphological stability, suitable triplet energy level, and equal charge carrier mobilities of hole and electron to form the broad carrier recombination zone in the emitting layer, thus reducing the triplet-triplet annihilation and resulting in a slight efficiency roll off of 0.5% from the brightness of 1 and 1000cd/m2. This work also systematically investigated the arrangement of the POAPF:FIrpic recombination zone for optimizing the performance of the single layer PHOLED.

General application of blade coating to small-molecule hosts for organic light-emitting diode

Blade coating is applied to multi-layer phosphorescent OLED with five small-molecule hosts for the emission layer, including bis[3,5-di (9H-carbazol-9-yl)phenyl]diphenylsilane (SimCP2), 2,6-bis(3-(9H-carbazol-9-yl)phenyl) pyridine (26DCzPPy), 4,4′,4″-tris-(N-carbazolyl)-triphenylamine (TCTA), 9,9-bis[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]fluorene (TBCPF), and 2,7-bis(diphenylphosphoryl)-9,9′-spirobi[fluorene] (SPPO13). In general, blade coating gives low surface roughness around 0.2nm without phase separation of the emitter and the host. In the large area of 2cm by 3cm the film thickness distribution is within 10% and uniform light-emission is achieved. 1,3-Bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene (OXD-7) is added to tune the electron transport. Among all the hosts, 26DCzPPy and SimCP2 have by far the best electron–hole balance and consequently show the highest efficiency. For SimCP2, the maximal efficiency is 15.8cd/A for blue and 24.2cd/A for white emission. The order of efficiencies for the hosts is found to be quite different from the order in vacuum evaporation for the same device structures.

ChemInform Abstract: Small Molecule Host Materials for Solution Processed Phosphorescent Organic Light‐Emitting Diodes.

AbstractReview: 86 refs.

Small molecule host materials for solution processed phosphorescent organic light-emitting diodes.

Solution processed phosphorescent organic light-emitting diodes (OLEDs) have been actively developed due to merits of high quantum efficiency of phosphorescent materials and simple fabrication processes of solution processed OLEDs. The device performances of the solution processed phosphorescent OLEDs have been greatly improved in the last 10 years and the progress of the device performances was made by the development of small molecule host materials for solution processes. A hybrid host of polymer and small molecules, a single small molecule host and a mixed host of small molecule hosts have effectively enhanced the quantum efficiency of the solution processed phosphorescent OLEDs. Therefore, this paper reviews recent developments in small molecule host materials for solution processed phosphorescent OLEDs and provides future directions for the development of the small molecule host materials.

Novel tri-carbazole modified fluorene host material for highly efficient solution-processed blue and green electrophosphorescent devices

A series of novel solution-processable small-molecule host materials: 2DPF-TCz, 2SBF-TCz, 27DPF-TCz, and 27SBF-TCz comprising a fluorene monomer as the rigid core and tri-carbazole as the periphery have been designed and synthesized, and their optical, electrochemical, and thermal properties have been fully characterized. The host materials exhibit high glass-transition temperatures (231–310 °C) and high triplet energy levels (2.61–2.73 eV). High-quality amorphous thin films can be obtained by spin-coating the host materials from solutions. It is found that the HOMO level of the host materials can be tuned by linking the tri-carbazole unit to the 2,7 positions of the fluorine core, resulting in appropriate HOMO energy levels (−5.36 to −5.23 eV) for improved hole-injection in the device. Solution-processed blue and green electrophosphorescent devices bases on the developed host materials exhibit high efficiencies of 21.2 and 34.8 cd A−1, respectively.

Synthesis and characterization of novel 2,7-carbazole derivatives for blue light-emitting diodes

Two 2,7-carbazole based low molecular weight derivatives, 9-hexyl-N 2,N 2,N 7,N 7-tetraphenyl-carbazole-2,7-diamine (TPCA) and 9′-hexyl-9′H-9,2′:7′,9″-tercarbazole (HTC), were synthesized by Buchwald and Ullmann coupling reactions, respectively. The optical, electrochemical and thermal properties of this two analogous small molecule hosts have been characterized. The HOMO level of TPCA and HTC were −5.25 and −5.29 eV indicating good hole-transporting properties. Both of the compounds emit deep blue light peaked at 410 and 428 nm in solid state. According to the measurement, the luminescence quantum yield of TPCA is 0.98, almost 1.7 times higher than that of HTC (0.59) in dilute THF solution. The geometrical and electronic properties of the compounds were studied using density functional theory calculations. The studies mentioned above indicate that both TPCA and HTC are suitable for active materials of blue light-emitting diodes.

Comparison of light out-coupling enhancements in single-layer blue-phosphorescent organic light emitting diodes using small-molecule or polymer hosts

Single-layer blue phosphorescence organic light emitting diodes (OLEDs) with either small-molecule or polymer hosts are fabricated using solution process and the performances of devices with different hosts are investigated. The small-molecule device exhibits luminous efficiency of 14.7 cd/A and maximum power efficiency of 8.39 lm/W, which is the highest among blue phosphorescence OLEDs with single-layer solution process and small molecular hosts. Using the same solution process for all devices, comparison of light out-coupling enhancement, with brightness enhancement film (BEF), between small-molecule and polymer based OLEDs is realized. Due to different dipole orientation and anisotropic refractive index, polymer-based OLEDs would trap less light than small molecule-based OLEDs internally, about 37% better based simulation results. In spite of better electrical and spectroscopic characteristics, including ambipolar characteristics, higher carrier mobility, higher photoluminescence quantum yield, and larger triplet state energy, the overall light out-coupling efficiency of small molecule-based devices is worse than that of polymer-based devices without BEF. However, with BEF for light out-coupling enhancement, the improved ratio in luminous flux and luminous efficiency for small molecule based device is 1.64 and 1.57, respectively, which are significantly better than those of PVK (poly-9-vinylcarbazole) devices. In addition to the theoretical optical simulation, the experimental data also confirm the origins of differential light-outcoupling enhancement. The maximum luminous efficiency and power efficiency are enhanced from 14.7 cd/A and 8.39 lm/W to 23 cd/A and 13.2 lm/W, respectively, with laminated BEF, which are both the highest so far for single-layer solution-process blue phosphorescence OLEDs with small molecule hosts.

Solution processed phosphorescent white organic light emitting diodes using a small molecule host material

Highly efficient phosphorescent white organic light-emitting diodes (PHWOLEDs) were developed using a solution processed 9-(3-(dibenzo[b,d]furan-2-yl)phenyl)-9H-carbazole (CzDBF) host material. Blue and orange phosphorescent emitters were doped into the CzDBF host and balanced blue and orange emission was obtained. High quantum efficiency of 13.2% was achieved in the solution processed PHWOLEDs using the CzDBF host material.

Glass‐transition temperatures of nanostructured amorphous bulk polymers and their blends

ABSTRACTNanostructured amorphous bulk polymer samples were produced by processing them with small molecule hosts. Urea (U) and gamma‐cyclodextrin (γ‐CD) were utilized to form crystalline inclusion compounds (ICs) with low and high molecular weight as‐received (asr‐) poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA), and their blends as included guests. Upon careful removal of the host crystalline U and γ‐CD lattices, nanostructured coalesced (c‐) bulk PVAc, PMMA, and PVAc/PMMA blend samples were obtained, and their glass‐transition temperatures, Tgs, measured. In addition, non‐stoichiometric (n‐s)‐IC samples of each were formed with γ‐CD as the host. The Tgs of the un‐threaded, un‐included portions of their chains were observed as a function of their degree of inclusion. In all the cases, these nanostructured PVAc and PMMA samples exhibited Tgs elevated above those of their as‐received and solution‐cast samples. Based on their comparison, several conclusions were reached concerning how their molecular weights, the organization of chains in their coalesced samples, and the degree of constraint experienced by un‐included portions of their chains in (n‐s)‐γ‐CD‐IC samples with different stoichiometries affect their chain mobilities and resultant Tgs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1041–1050

Highly efficient red phosphorescent organic light-emitting diodes based on solution processed emissive layer

Highly efficient red phosphorescent organic polymer light-emitting diodes (PhOLEDs) were fabricated based on a solution-processed small-molecule host 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) by doping an iridium complex, tris(1-(2,6-dimethylphenoxy)-4-(4-chlorophenyl)phthalazine)iridium (III) (Ir(MPCPPZ)3). A hole blocking layer 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBI) with a function of electron transport was thermally deposited onto the top of CBP layer. The diode with the structure of ITO/PEDOT:PSS (50nm)/CBP:Ir(MPCPPZ)3 (55nm)/TPBI (30nm)/Ba (4nm)/Al (120nm) showed an external quantum efficiency (QEext) of 19.3% and luminous efficiency (LE) of 18.3cd/A at a current density of 0.16mA/cm2, and Commission International de I'Eclairage (CIE) coordinates of (0.607, 0.375). It was suggested that the diodes using TPBI layer exhibited nearly 100% internal quantum efficiency and one order magnitude enhanced LE or QEext efficiencies.

Fluorescent polymer guest:small molecule host solution-processed OLEDs

Solution-processed OLEDs with polymer hosts and polymer or small-molecule guests have been studied extensively. More recently, efficient solution-processed OLEDs with small molecule hosts and small molecule guests were also reported. However, small molecule hosts of polymer guests in solution-processed fluorescent OLEDs have not been investigated. In this work guest:host systems consisting of the small molecule 4,4′-bis(9-carbazolyl)-biphenyl (CBP) as host to polymer guests such as novel benzobisoxazole (BBO)-containing copolymers and well-known poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) are compared to those with poly(N-vinyl carbazole) (PVK) host, which previously yielded highly efficient phosphorescent OLEDs. In the case of MEH-PPV, guest:host OLEDs are also compared to those with a neat MEH-PPV emitting layer. It is found that replacing the polymer host PVK with the small molecule host CBP improves efficiencies by up to 100%. A blue emissive BBO-polymer:CBP device reaches a luminous efficiency (ηL,max) of 3.4 cd A−1 (external quantum efficiency ηext = 2.4%), while the PVK-based device exhibits ηL,max = 1.7 cd A−1 (ηext = 1.2%). A green emissive BBO:CBP OLED exhibits ηL,max = 5.7 cd A−1 (ηext = 2.1%), while that in the PVK host is 3.1 cd A−1 (ηext = 1.1%). For MEH-PPV:CBP these values are 3.7 cd A−1 (ηext = 1.4%), compared to 2.9 cd A−1 (ηext = 1.0%) for MEH-PPV:PVK and 0.7 cd A−1 (ηext = 0.4%) for the neat MEH-PPV device. Possible origins of the improvement are discussed, including increased charge mobility, smoother film morphology, and the potential effect of multiple non-coiling host small molecules (in contrast to the likely coiled PVK) surrounding a polymer guest.