Effect Of Intermolecular Interactions Research Articles

Strengthening Near‐Infrared Photon Harvesting in Semi‐Transparent All‐Polymer Solar Cells through the Synergy of Fluorination on the Selenide Monomer Backbone

AbstractAll‐polymer solar cells (all‐PSCs) offer promising potential for large‐scale manufacturing due to their remarkable mechanical and thermal stability. However, the limited capacity of polymer acceptors for near‐infrared (NIR) photon harvesting has impeded their progress in semi‐transparent (ST) all‐PSCs. Here, the study develops a pair of new NIR polymer acceptors, named PYSeF‐T and PYSe2F‐T, with mono‐/di‐fluorinated end groups capped to the selenide monomer backbone, respectively. Owing to the stronger intermolecular interaction and intramolecular charge transfer effect of the di‐fluorinated end groups with the selenide backbone, PYSe2F‐T exhibits a stronger crystallinity and a more bathochromic absorption to 1000 nm. When blended with the donor, PM6, the PY2SeF‐T‐based all‐PSC demonstrates a higher efficiency of 16.73% with a remarkable short‐circuit current (JSC) of 27.7 mA cm−2, which is the highest JSC for all‐PSCs. Based on these, the ST device based on PM6:PYSe2F‐T demonstrates a superior efficiency of 12.52% with an average visible transmittance of 26.2% and a light utilization efficiency of 3.28%, outperforming the mono‐fluorinated counterpart. The work provides an in‐depth understanding of the above synergistic effects to develop NIR polymer acceptors and establishes a solid foundation for future investigations into large‐area and flexible ST all‐PSCs.

Low‐Cost, Large‐Area, and Highly Transparent Organic Glassy Scintillators for High Resolution X‐Ray Imaging

AbstractThe architectural design and fabrication of low‐cost, high‐performance organic scintillators are critical for medical imaging and material/device analysis. However, achieving large‐area and high‐transparency organic scintillators in a low‐cost and easy‐to‐implement method remains a challenge. Herein, a new design strategy for regulating the side chain length of maleimide derivatives is demonstrated to develop organic scintillators for achieving low‐cost, large‐area, and high spatial resolution in X‐ray imaging. The effective intermolecular interactions and relatively twisted molecular structure endow PAM‐M4 molecule with outstanding scintillator properties. More importantly, as demonstrated for the first time, pure organic glassy films with a diameter over 10 cm and high optical transparency can be prepared by the developed melt‐quenched method using PAM‐M4 crystal powder as a raw material. This glassy film exhibits excellent X‐ray imaging ability with a spatial resolution as high as 27.0 lp mm−1 at MTF = 0.20, which is one of the best results among reported organic scintillators. The results of this work not only develop a new design strategy for high‐performance organic scintillators but also demonstrate a reliable approach to fabricating large area screens with superior spatial resolution for medical or industrial X‐ray imaging applications.

Experimental and simulation study on the solubility of 1-naphthylamine in twelve neat solvents

To meet the demand of separating and purifying 1-naphthylamine from the reaction production and filling the solubility data gap, the solubility of 1-naphthylamine in twelve pure solvents (acetone, acetonitrile, ethyl acetate, n-butyl acetate, cyclohexane, n-heptane, methanol, ethanol, n-propanol, iso-propanol, n-butanol, and iso-butanol) was experimentally investigated in the range from 273.15 K to 308.15 K. It was found that the solubility of 1-naphthylamine increases markedly with increasing temperature in all solvent systems. The maximum solubility was 0.8978 (in the solvent of acetone,T = 308.15 K) and the minimum solubility was 0.005485 (in the solvent of n-heptane, T = 273.15 K). Then the experimental solubility data was correlated by the modified Apelblat model, Van't Hoff model, NRTL model, Wilson model, and Margules model. ARD% was calculated to assess the accuracy of the five equations and the results indicated that the modified Apelblat model fits optimally with an average ARD% value of 1.62 %. The effects of various physicochemical properties such as solvent polarity, hydrogen bond donor, hydrogen bond acceptor, and cohesive energy density on solute dissolution behavior were explored. In addition, the apparent thermodynamic properties of 1-naphthylamine in different solvents were analyzed based on modified Van’t Hoff model, which indicated the dissolution process of 1-naphthylamine in selected solvents is endothermic and entropy-driving. Finally, the effect of intermolecular interactions on the dissolution behavior was investigated at the molecular scale through molecular dynamics simulation studies, including molecular electrostatic potential surface, solvation free energy and radial distribution function analysis. This work will provide a fundamental guidance for the crystallization, separation, and purification of 1-naphthylamine.

Experimental and molecular simulation analysis of the dissolution behavior of Musk ambrette in organic solvents

The solubility of Musk ambrette in i-propanol (IPA), i-butanol (IBA), n-heptane (HPT), n-hexane (HX), cyclohexane (CYH), methyl acetate (MAC), ethyl acetate (EAC), acetone (ACE), IPA + ACE at 278.15 K to 318.15 K was determined. The mole fraction solubility of Musk ambrette in pure IPA at the temperature of 298.15 K were found to be 0.9492 × 10-2 mol·mol−1. The difference is that the solubility of Musk ambrette in ACE reaches 0.2257 mol·mol−1, which is much higher than the solvent mentioned above. The strong intermolecular hydrogen bonding formed by IPA resulted in its lowest solvation capacity for Musk ambrette. In addition, to further investigate the solubility pattern of Musk ambrette, we used 8 models (Van’t Hoff, modified Apelblat, Buchowski-Ksiazczak, Yaws, NRTL, Wilson, Jouyban-Acree and Sun model) to fit and obtain a general equation for solubility versus temperature. These results yielded a large amount of statistically significant data. Comparisons revealed that the modified Apelblat and Yaws equation showed the least deviation in forecasting solubility variations with temperature. Meanwhile, we proved that the dissolution of Musk ambrette is a heat-absorbing entropy increasing process by Van't Hoff equation calculation. ΔsolGo for the 12 solvents is in the following order: ACE < MAC < EAC < w = 0.2007 < w = 0.4025 < w = 0.6076 < CYH < w = 0.8070 < HPT < HX < IBA < IPA. ΔsolGo is smaller the easier it dissolves, which is consistent with the law of dissolution. Secondly, we performed thermal analysis and X-ray diffraction tests on Musk ambrette crystals prepared in different solvents, which showed that none of the several systems investigated led to the creation of new crystalline forms or solvatoids, further confirming the suitability of the solvents. Besides, we discuss the correspondence between solubility and the HSP, π, α, β, and CED of the solvents and thus tentatively confirm the significant influence of the solvent properties on solubility. The principle of similarity and compatibility is satisfied for most of the solvents. In particular, the CED values of the larger solvents were not favorable for the solubilization of Musk ambrette. We also analyzed the molecular surface electrostatic potential of Musk ambrette by visualization techniques. Finally, IPA and ACE and their binary solution systems were analyzed by molecular dynamics simulations. The effect of solvent intermolecular interactions on the solubilization pattern was discussed. It was further confirmed that weak interactions of solvent molecules contribute more to the dissolution of Musk ambrette. These findings suggest that the prediction of solvent solubility can be initially achieved by molecular simulation techniques. Undoubtedly, this study will furnish a valuable information for the purification of Musk ambrette.

Appending Coronene Diimide with Carbon Nanohoops Allows for Rapid Intersystem Crossing in Neat Film

AbstractThe development of innovative triplet materials plays a significant role in various applications. Although effective tuning of triplet formation by intersystem crossing (ISC) has been well established in solution, the modulation of ISC processes in the solid state remains a challenge due to the presence of other exciton decay channels through intermolecular interactions. The cyclic structure of cycloparaphenylenes (CPPs) offers a unique platform to tune the intermolecular packing, which leads to controllable exciton dynamics in the solid state. Herein, by integrating an electron deficient coronene diimide (CDI) unit into the CPP framework, a donor‐acceptor type of conjugated macrocycle (CDI‐CPP) featuring intramolecular charge‐transfer (CT) interaction was designed and synthesized. Effective intermolecular CT interaction resulting from a slipped herringbone packing was confirmed by X‐ray crystallography. Transient spectroscopy studies showed that CDI‐CPP undergoes ISC in both solution and the film state, with triplet generation time constants of 4.5 ns and 238 ps, respectively. The rapid triplet formation through ISC in the film state can be ascribed to the cooperation between intra‐ and intermolecular charge‐transfer interactions. Our results highlight that intermolecular CT interaction has a pronounced effect on the ISC process in the solid state, and shed light on the use of the characteristic structure of CPPs to manipulate intermolecular CT interactions.

Appending Coronene Diimide with Carbon Nanohoops Allows for Rapid Intersystem Crossing in Neat Film.

The development of innovative triplet materials plays a significant role in various applications. Although effective tuning of triplet formation by intersystem crossing (ISC) has been well established in solution, the modulation of ISC processes in the solid state remains a challenge due to the presence of other exciton decay channels through intermolecular interactions. The cyclic structure of cycloparaphenylenes (CPPs) offers a unique platform to tune the intermolecular packing, which leads to controllable exciton dynamics in the solid state. Herein, by integrating an electron deficient coronene diimide (CDI) unit into the CPP framework, a donor-acceptor type of conjugated macrocycle (CDI-CPP) featuring intramolecular charge-transfer (CT) interaction was designed and synthesized. Effective intermolecular CT interaction resulting from a slipped herringbone packing was confirmed by X-ray crystallography. Transient spectroscopy studies showed that CDI-CPP undergoes ISC in both solution and the film state, with triplet generation time constants of 4.5 ns and 238 ps, respectively. The rapid triplet formation through ISC in the film state can be ascribed to the cooperation between intra- and intermolecular charge-transfer interactions. Our results highlight that intermolecular CT interaction has a pronounced effect on the ISC process in the solid state, and shed light on the use of the characteristic structure of CPPs to manipulate intermolecular CT interactions.

The Effect of Intermolecular Interactions on the Dissolution Property of Aripiprazole

The Effect of Intermolecular Interactions on the Dissolution Property of Aripiprazole

Effects of polyurethane/functionalised carbon nanotube interfacial interactions on tensile and compressive properties – molecular dynamics simulations

In order to understand the enhancement mechanism of the interaction between functionalised carbon nanotubes and polymer matrix, and to investigate the effects of different functionalised carbon nanotubes on the properties of composites at the microscopic level, the models of pure polyurethane (PUR), carbon nanotubes/polyurethane (CNTs/PUR), hydroxyl-functionalised carbon nanotubes/polyurethane (CNTOH/PUR), and carboxyl-functionalised carbon nanotubes/polyurethane (CNTCOOH/PUR) systems were constructed, and molecular dynamics methods were used to simulate the effects of different functionalised carbon nanotubes on the mechanical properties of polyurethane composite systems. The effects of different functionalised carbon nanotubes on the properties of PUR composite systems were compared by analysing the properties of PUR and its composite systems in terms of free volume fraction (FFV), radial distribution function (RDF), binding energy, and density distribution of PUR around different functionalised carbon nanotubes. The effects of intermolecular interactions on the properties of the composite systems were elucidated at the microscopic level. The final simulation results show that the CNTCOOH/PUR composite system with added carboxylated CNTs has the highest tensile yield strength, compressive properties and modulus; the smallest free volume fraction; the strongest bonding energy between CNTCOOH and PUR matrix, the largest density distribution of PUR matrix around CNTCOOH, and the best interfacial interaction.

Dynamic behaviors of delaminated nanofilms partly bonded on substrates with sub-nanoscale van der Waals dynamic boundaries

Abstract Dynamic buckling-induced delamination of nanofilms on substrates is a universal and essential phenomenon in nanoelectromechanical systems (NEMS). Van der Waals (vdWs) interactions play an important role in the dynamic buckling-induced delamination of nanofilms on substrates due to the interaction distances at nanoscale or even sub-nanoscale in NEMS. Therefore, it is interesting yet challenging to reveal the effect of intermolecular vdWs interactions on dynamic buckling-induced delamination of nanofilms on substrates. By considering sub-nanoscale dynamic boundary effects induced by intermolecular vdWs interactions, a parametric excitation nonlinear vibration model for dynamic buckling-induced delamination of nanofilms partly bonded on substrates is established. Effects of sub-nanoscale vdWs dynamic boundaries on transient and steady-state responses of dynamically delaminated nanofilms on substrates are analyzed. The sub-nanoscale vdWs dynamic boundaries lead the dynamic responses of delaminated-nanofilm/substrate systems very sensitive to initial conditions. The bending and shifting frequency response results demonstrated that the system nonlinearities can be greatly amplified by the sub-nanoscale vdWs dynamic boundary effect. Moreover, the spontaneous symmetry breaking and violent interfacial tearing/healing phenomena can be also triggered in the systems. Based on spontaneous symmetry breaking, a trans-scale relationship between nanofilm equilibrium positions and intermolecular vdWs interactions is established, which can provide a promising route for trans-scale measurements of molecular scale interfacial interactions. The work can also be helpful for the dynamic design of resonant NEMS devices based on nanofilm/substrate systems.

A review on the influence of various metal oxide nanoparticles on structural, morphological, optical, thermal and electrical properties of PVA/PVP blends

Biopolymer blend based nanocomposites have been interestingly investigated by researchers to achieve advanced composite functional materials that are environmentally amicable. Among the varieties of biopolymers, widespread attention has been given to polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) owing to their interesting properties like water solubility, biodegradability, biocompatibility and non-toxicity. PVA and PVP form a completely miscible blend at all compositions as both the polymers are rich in a variety of functional groups that permit effective intermolecular interactions between the polymers as well as with filler. PVA/PVP blend exhibits excellent dopant sensitive properties also. Metal oxide nanoparticles (MONPs) have made a prominent place in the area of scientific and technological research due to their unique chemical and physical properties. Doping with MONPs enhances the properties of the PVA/PVP blend matrix and the resulting PVA/PVP/MONP polymer nanocomposites are suitable for multifunctional purposes. This review mainly focused on the influence of various MONPs such as ZnO, CuO, Al2O3, ZrO2, MnO, SnO, MgO, TiO2, etc. in the structural, morphological, thermal, optical and electrical properties of PVA/PVP blend as well as its applications in various fields.

Low bandgap fused-ring electron acceptors based on π-expended asymmetric benzotrithiophene core: Regulating aggregation and photovoltaic performance by side chain isomerization

Asymmetric molecular design strategy has received increasing attention in the development of fused-ring electron acceptors (FREAs). Benzo [2,1-b: 3,4-b’: 5,6-b”] trithiophene (asym-BTT) with intrinsically asymmetric and electron-rich π-plane is an ideal unit to construct asymmetric FREAs, whereas asym-BTT-based FREAs are still very limited. Herein, two asymmetric FREAs based on the π-expended asym-BTT fused-core with para-hexylphenyl and meta-hexylphenyl side chains (p-FABTT and m-FABTT) have been developed. Owing to strong electron-donating ability and planar configuration of π-expended asym-BTT fused-core, two acceptors exhibit effective intramolecular charge transfer and intermolecular interaction, leading to near infrared absorption above 900 nm with narrow bandgaps of around 1.34 eV. Although the same π-conjugated backbones of two acceptors afford the nearly identical energy levels and solution absorptions, side chain isomerization leads to significant differences in film absorption, molecular stacking orientation and crystallinity. In neat film, the m-FABTT with meta-hexylphenyl side chains exhibits slightly redshifted absorption with stronger 0-0 absorption peak from J-aggregation compared to p-FABTT with para-hexylphenyl side chains. More orderly molecular stacking and stronger π-π interactions with shorter π-π stacking distance in both the neat film and active layer can be observed for m-FABTT. When blended with donor polymer D18, m-FABTT exhibits broadened spectral region and proper phase separation morphology for effective exciton dissociation and charge transport. Therefore, the OSCs device based on m-FABTT achieves an optimal PCE of 7.14 % with a higher JSC of 15.39 mA cm−2 and an improved FF of 57.96 % as comparing with p-FABTT-based device (a PCE of 4.81 % with a JSC of 11.67 mA cm−2 and a FF of 48.51 %).

Experimental determination of relationship between intramolecular bond lengths and their stretching vibrational frequencies of N,N-dimethylformamide and acetonitrile molecules in the liquid state

Abstract Time-of-flight (TOF) neutron diffraction measurements have been carried out on pure liquid deuterated N,N-dimethylformamide (DMF-d7), acetonitrile (AN-d3), and their concentrated LiTFSA solutions to investigate the effect of intermolecular interaction to intramolecular bond lengths, rCO, of the DMF and rCN of the AN molecules in the liquid state. Intramolecular parameters of DMF and AN are determined by least-squares fitting analyses of neutron total interference terms observed in the high-Q region. Attenuated total reflection (ATR) IR spectra have been measured for pure liquid DMF, AN, and their LiTFSA solutions of natural abundances to determine the average C=O and C≡N stretching vibrational frequencies (νCO and νCN) of the DMF and AN molecules, respectively. The relationships between rCO and νCO for DMF, and between rCN and νCN for AN, are well approximated by linear functions. The value, dνCO/drCO = −3,400 ± 1,600 cm−1 Å−1 has been derived for DMF from the slope of the fitted function. dνCN/drCN = −7,000 ± 3,000 cm−1 Å−1 has been obtained for AN. It has been revealed that the C = O bond length of the DMF and the C≡N one of the AN molecules are sensitively affected by intermolecular interaction.

The Effect of Intermolecular Interactions between Aromatic Ring‐Containing Insulators and Semiconductors in Pentacene Thin‐Film Transistors

AbstractMobility is an important parameter to estimate the performance of organic thin‐film transistors, one of the key factors affecting the mobility is the first several semiconductors molecular layers near the insulator surface. A strategy is proposed to introduce aromatic‐rings in the gate insulating layer to modulate the growth of pentacene, thus a series of aryl group containing polymers by reversible‐addition‐fragmentation chain‐transfer polymerization is synthesized for the preparation of organic thin‐film transistor insulators. The semiconductor layer is evaporated on the polymer insulators at room temperature. As the inducing function of the aromatic ring, greater weak interactions between dielectric materials and semiconductors by simulation, which makes the initial pentacene layer weak epitaxial growth, therefore pentacene could form better morphology, especially larger crystal domains and uniform thin‐film continuity. The results show that precision design and synthesis of polymer insulator layers provide new methods to achieve high performance of organic thin‐film transistors with easier fabricating process.

Insights into the Mechanism of Tryptophan Fluorescence Quenching due to Synthetic Crowding Agents: A Combined Experimental and Computational Study.

Intrinsic tryptophan fluorescence spectroscopy is an important tool for examining the effects of molecular crowding and confinement on the structure, dynamics, and function of proteins. Synthetic crowders such as dextran, ficoll, polyethylene glycols, polyvinylpyrrolidone, and their respective monomers are used to mimic crowded intracellular environments. Interactions of these synthetic crowders with tryptophan and the subsequent impact on its fluorescence properties are therefore critically important for understanding the possible interference created by these crowders. In the present study, the effects of polymer and monomer crowders on tryptophan fluorescence were assessed by using experimental and computational approaches. The results of this study demonstrated that both polymer and monomer crowders have an impact on the tryptophan fluorescence intensity; however, the molecular mechanisms of quenching were different. Using Stern-Volmer plots and a temperature variation study, a physical basis for the quenching mechanism of commonly used synthetic crowders was established. The quenching of free tryptophan was found to involve static, dynamic, and sphere-of-action mechanisms. In parallel, computational studies employing Kohn-Sham density functional theory provided a deeper insight into the effects of intermolecular interactions and solvation, resulting in differing quenching modes for these crowders. Taken together, the study offers new physical insights into the quenching mechanisms of some commonly used monomer and polymer synthetic crowders.

Transformation of Highly Hydrophobic Triarylphosphines into Amphiphiles via Staudinger Reaction with Hydrophilic Trichlorophenyl Azide.

Owing to its hydrophobic properties and reactivity, triarylphosphines (PAr3 ) are promising precursors for the development of new amphiphiles. However, an efficient and reliable synthetic method for amphiphiles based on highly hydrophobic PAr3 is still required. Herein, a straightforward transformation of highly hydrophobic PAr3 into amphiphiles via the Staudinger reaction is reported. By simply mixing PAr3 and a hydrophilic trichlorophenyl azide containing two hydrophilic chains, amphiphiles bearing a N=P bond (i. e., an azaylide moiety) were quantitatively formed. The obtained azaylide-based amphiphiles were remarkably water-soluble, enabling their spontaneous self-assembly into 2 nm-sized micelles composed of 4-5 molecules in water with a low critical micelle concentration (up to 0.05 mM or less) due to the effective intermolecular interactions among the hydrophobic surfaces. Although the azaylide moiety is easily hydrolyzed in the presence of water, the azaylide in the amphiphiles displayed notable stability in water even at 60 h, which stems from the LUMO modulation induced by the presence of three electron-withdrawing chloro groups and two twisted alkoxycarbonyl groups, according to DFT calculations. An amphiphile having a large hydrophobic surface solubilized various hydrophobic organic dyes through efficient intermolecular interactions, resulting in the dyes exhibiting either monomer or excimer emissions in water.

Effect of intermolecular interactions on the glass transition temperature of chemically modified alternating polyketones

Thermal properties of polymers depend on the chemical structure of the polymer chain and intermolecular forces arising from hydrogen bonding and π-π stacking. Here we analyzed the effect of increasing the amount of supramolecular interactions on the glass transition temperature of polyketones by chemically modifying the same polymer backbone with five amine derivatives, namely (1-(3-aminopropyl)-imidazole, 4-(aminomethyl) benzoic acid, 6-aminohexanoic acid, benzylamine or hexylamine, at various molar concentrations. The grafting was performed via the Paal-Knorr reaction and the interactions between the pyrrole backbone and different grafted functional groups were elucidated by proton nuclear magnetic resonance, Fourier transform infrared and X-ray photoelectron spectroscopy as well as differential scanning calorimetry and computational modeling. The modification of polyketone with 4-(aminomethyl) benzoic acid and 6-aminohexanoic acid, allowed for new possibilities of hydrogen bonding and led to a significant increase in the glass transition temperature as compared to the neat polymer and pyrrole-containing polymers that did not bear reactive side groups. In contrast, modification with the imidazole derivative was found to introduce new and more robust CH⋯π interactions between imidazole groups and the π-system of the pyrrole backbone chain, based on electrostatic effects. Both types of supramolecular interactions affect the mobility of the backbone chains and this systematic study demonstrates how the combined effect of π-π stacking and hydrogen bonding to carboxylate moieties can be used to tune the molecular mobility and phase transition temperature of these chemically modified polyketones.

Intermolecular interactions between nucleoside, amino acid, and water molecules probed by ultraviolet photodissociation in the gas phase

The effects of intermolecular interactions on the reactivity of hydrogen-bonded clusters of adenosine and tryptophan (Trp) in the gas phase were investigated by water adsorption and ultraviolet photoexcitation. The product ion spectra of photoexcited H+(Trp)(adenosine) and its hydrated clusters were obtained at 8 K using a tandem mass spectrometer equipped with an electrospray ionization source and a cold ion trap. The primary product ion of photoexcitated H+(Trp)(adenosine) was H+(adenine), which was formed via Trp detachment and glycosidic bond cleavage of adenosine. The primary product ion formed after the photoexcitation of H+(Trp)(adenosine)(H2O)n was H+(adenosine), which resulted from the detachment of Trp and water molecules. The relative abundance of H+(adenosine) was substantially higher than that of H+(adenine), indicating that water adsorption on H+(Trp)(adenosine) weakened the intermolecular interactions between Trp and adenosine and inhibited the photoinduced glycosidic bond cleavage of adenosine in the clusters.

Strategic molecular engineering of blue phosphorescent Pt(II)compounds for the development of high-efficiency single-doped white OLEDs

We synthesized two novel Pt(Ⅱ) β-diketonate compounds, 2′,6′-dimethoxy-4-tert-butyl-2,3′-bipyridinato-N,C4′)platinum(Ⅱ)(acetylactonate-O,O) (1) and 2′,6′-dimethoxy-4-trimethylsilyl-2,3′-bipyridinato-N,C4′)platinum(Ⅱ)(acetylactonate-O,O) (2), to develop blue phosphorescent compounds and systematically investigated their photoluminescent and electroluminescent characteristics. The compounds 1 and 2 exhibited bright sky-blue phosphorescence, with a phosphorescence maximum (λmax) at 465 nm and 475 nm, respectively. The luminescence quantum yields were found to be 0.63 for 1 and 0.93 for 2. At high concentrations, both compounds exhibited bright red emission originating from the formation of excimer. However, compound 2, due to effective intermolecular interactions, exhibited a more red-shifted emission than compound 1 at the same concentration.For fabricating phosphorescent organic light-emitting diodes, the compounds 1 and 2 were used as dopants, and a 50:50 mixture of 3′-di(9H-carbazol-9-yl)-1,1′-biphenyl:9-(3′-carbazol-9-yl-5-cyano-biphenyl-3-yl)-9H-carbazole-3-carbonitrile was used as the mixed host. When doped with 20 wt% of compound 2, the electroluminescent device exhibited the best performance, achieving an external quantum efficiency (EQE) of 13.7% at 100 cd/m2 and current efficiency of 35.5 cd A−1. Remarkably, the single-doped compound 2-based device achieved emission with Commission Internationale de L'Eclairage coordinates (x, y) of (0.40, 0.48). To the best of our knowledge, this is one of the highest performing single-doped white organic light-emitting diodes.

Upgrade of D+ software for hierarchical modeling of X-ray scattering data from complex structures in solution, fibers and single orientations.

This article presents an upgrade of the D+ software [Ginsburg et al. (2019 ▸). J. Appl. Cryst. 52, 219-242], expanding its hierarchical solution X-ray scattering modeling capabilities for fiber diffraction and single crystallographic orientations. This upgrade was carried out using the reciprocal grid algorithm [Ginsburg et al. (2016 ▸). J. Chem. Inf. Model. 56, 1518-1527], providing D+ its computational strength. Furthermore, the extensive modifications made to the Python API of D+ are described, broadening the X-ray analysis performed with D+ to account for the effects of the instrument-resolution function and polydispersity. In addition, structure-factor and radial-distribution-function modules were added, taking into account the effects of thermal fluctuations and intermolecular interactions. Finally, numerical examples demonstrate the usage and potential of the added features.

Geometric Signatures as Important Factors to Control the Photo-Stabilities of the Phosphorescent Pd(II)/Pt(II) Complexes: A Case Study.

Operation lifetime, as an important parameter, determines the performance of phosphorescent organic light-emitting diodes (OLEDs). Unveiling the intrinsic degradation mechanism of emission material is crucial for improving the operation's lifetime. In this article, the photo-stabilities of tetradentate transition metal complexes, the popular phosphorescent materials, are explored by means of density functional theory (DFT) and time-dependent (TD)-DFT, aiming to illustrate the geometric signatures as important factors to control the photo-stabilities. Results indicate that for the tetradentate Ni(II), Pd(II), and Pt(II) complexes, the coordinate bonds of the Pt(II) complex exhibit stronger strength. It seems that the strengths of coordinate bonds are closely related to the atomic number of the metal center in the same group, which could be attributed to the various electron configurations. The effect of intramolecular and intermolecular interactions on ligand dissociation is also explored here. The large intramolecular steric hindrance and strong π-π interaction between the Pd(II) complexes caused by aggregation could effectively raise the energy barriers of the dissociation reaction, leading to an unfeasible reaction pathway. Moreover, the aggregation of Pd(II) complex can change the photo-deactivation mechanism as compared to that of monomeric Pd(II) complex, which is favored for avoiding the TTA (triplet-triplet annihilation) process.