Effect Of Substituent Position Research Articles

Isomeric Covalent Organic Frameworks for High-Efficiency Photocatalytic CO2 Reduction: Substituent Position Effect.

The exploration of covalent organic frameworks (COFs) for high-efficiency photocatalytic CO2 reduction is urgently demanded. Herein, COF-based catalysts are constructed for the selective photoreduction of CO2 to CO via delicately designed isomeric monomers with substituent at the 4,5,9,10- positions (K) or 1,3,6,8-positions (A) of pyrene knots. The distinct substituted regions significantly affect the planarity of pyrene knots, resulting in COFs with different microstructures and photocatalytic activities. While employing a 5 W LED white-light as the light source, the single atomic Co contained A-Py-Bpy-COF-Co showcased a moderate CO evolution rate of 2174.4 µmol g-1 h-1. In sharp contrast, K-Py-Bpy-COF-Co reveals a considerable CO photo-reduction rate of 12 476.4 µmol g-1 h-1 (5.7 times higher than A-Py-Bpy-COF) with a selectivity up to 93.3%. Remarkably, the excellent photocatalytic activity of K-Py-Bpy-COF-Co can be maintained for at least 5 cycles without obvious decay. The distinct photocatalytic properties of the two isomeric COFs can be attributed to the larger steric-hindrance of K-Py-4CHO which enlarges the interlayer distances to inhibit exciton quenching and electron-richer nature of monatomic Co in K-Py-Bpy-COF-Co. This work provides a new protocol to explore COFs with boosted photocatalytic performance via isomeric design from refined modulation of reported COFs.

Electrodeposition of Manganese (III) Phthalocyanine/ Reduced Graphene Oxide for Asymmetric Supercapacitor Devices.

In this study, two novel tetra-substituted manganese (III) phthalocyanines bearing (9H-carbazol-2-yl)oxy groups on peripheral (1) or non-peripheral (2) positions were prepared and used for modification of reduced graphene oxide (rGO) by applying a simple one-step electrodeposition technique for the first time. The manganese (III) phthalocyanines (MnPcs) were electropolymerized and graphene oxide was electrochemically converted into reduced graphene oxide simultaneously. Subsequently, an rGO-MnPc hybrid structure was formed directly on the NiF electrode (substrate) via layer-by-layer assembly. Additionally, the effect of substituent position on the charge storage capacity of the prepared hybrid capacitive candidates was investigated. The fabricated hybrid electrodes exhibited remarkable electrochemical performance due to the combination of manganese (III) phthalocyanines and reduced graphene oxide. The NiF/rGO2-2 electrode exhibited the highest specific capacitance (512.4 F g-1) at 0.5 A g-1 and the remained specific capacitance was obtained 88.1 % after 5000 consecutive charge-discharge cycles. An asymmetric supercapacitor (ASC) was constructed from rGO2-2 as the positive electrode and rGO as the negative electrode with a working potential of 1.5 V. The as-prepared device delivered a specific energy of 17.4 Wh kg-1 at 350 W kg-1. Hence, manganese (III) phthalocyanine-reduced graphene oxide electrodes can be considered outstanding materials for energy storage applications in the future.

Effect of hydrophilic group substituent position on adhesion at the emulsified asphalt/aggregate interface

Emulsified asphalt offers energy-saving and environmental benefits, aligning with low-carbon, high-quality development requirements. However, poor adhesion hampers the development of emulsified asphalt. The hydrophilic group substituent position significantly influences the adhesive strength at the emulsified asphalt/aggregate interface. To further elucidate this mechanism, this study employs molecular dynamics (MD) simulation techniques, focusing on the positional variations of the hydrophilic group in the sodium dodecylbenzene sulfonate molecule, particularly the SDBS2–1#, SDBS3–1#, and SDBS4–1# configurations. The objective is to enhance adhesion between these two materials. The simulation results were validated through macroscopic demulsification experiments, encompassing a comprehensive analysis of various parameters, including relative concentration distribution, diffusion coefficient, adhesion work, electron density difference, and electrostatic potential distribution. The result demonstrated a strong synergistic effect between the emulsifiers' molecular structure and the aggregates' chemical composition. The emulsifier SDBS4–1# with para-substitution enhances adhesion at the interface between the emulsified asphalt and alkaline aggregate (CaCO₃) by 50.4 %. The emulsifier SDBS2–1# with ortho-substitution enhances adhesion at the interface between the emulsified asphalt and acidic aggregate (SiO₂) by 33.3 %. Furthermore， the emulsifiers SDBS4–1# and SDBS2–1# promote the accumulation of electrons in asphalt molecules on CaCO₃ and SiO₂ surfaces, respectively. This increase in electron accumulation enhances the adhesion performance between emulsified asphalt and aggregate at their interface. Therefore, optimizing the structure of emulsifier molecules significantly increases the bonding strength between emulsified asphalt and aggregate surfaces.

Effect of substituent position on assembly of compounds bearing ortho/para over meta directing groups

This research investigated the impact of substituent location on intermolecular interactions and crystal packing. A class of N-(dichlorophenyl)-2-pyrazincarboxamide derivatives were synthesized and characterized: 2,5-dichloro (2,5-diCl), 3,4-dichloro (3,4-diCl), and 2,4-dichloro (2,4-diCl). Comparison with their monochloro counterparts (2-chloro (2-Cl), 3-chloro (3-Cl), and 4-chloro (4-Cl)) revealed a distinct structural variation upon introducing a second chlorine substituent at the ortho/para positions of the phenyl ring. Conversely, incorporating a second chlorine atom at the meta position resulted in similar molecular packing. These findings suggest that ortho/para directing groups play a dominant role in dictating the crystal assemblies of the studied compounds.

Visible Light-Driven Hydrogen Evolution Catalysis by Heteroleptic Ni(II) Complexes with Chelating Nitrogen Ligands: Probing Ligand Substituent Position and Photosensitizer Effects

This study aims to advance the field of green chemistry and catalysis by exploring alternatives to conventional non-renewable energy sources. Emphasis is placed on hydrogen as a potential fuel, with a focus on the catalytic properties of Ni(II) complexes when coordinated with o-phenylenediamine and diimine ligands. We report the synthesis and comprehensive characterization, with various physical and spectroscopic techniques, of three heteroleptic Ni(II) complexes: [Ni(1,10-phenanthroline)(o-phenylene diamine)] (1), [Ni(2,2-dimethyl-2,2-bipyridine)(o-phenylene diamine)] (2), and [Ni(5,5-dimethyl-2,2-bipyridine)(o-phenylene diamine)] (3). The catalytic activity of these complexes for hydrogen evolution was assessed through photochemical studies utilizing visible light irradiation. Two distinct photosensitizers, fluorescein and quantum dots, were examined under diverse conditions. Additionally, their electrocatalytic behavior was investigated to elucidate the hydrogen evolution reaction (HER) mechanism, revealing a combined proton-coupled electron transfer (PCET)/electron-coupled proton transfer (ECPT) mechanism attributed to the chemical nature of the diamine ligand. The influence of ligand substituent position, ligand chemical nature, and photosensitizer type on catalytic performance was systematically studied. Among the complexes investigated, complex 2 demonstrated superior catalytic performance, achieving a turnover number (TON) of 3357 in photochemical experiments using fluorescein as a photosensitizer. Conversely, complex 1 exhibited the highest TON of 30,066 for HER when quantum dots were employed as the photosensitizer.

Tuning the structure of pendant groups in poly(α‐arylTMC)s: A pathway to high glass transition temperature

AbstractAliphatic polycarbonates have been explored as environmentally benign alternatives to aromatic polycarbonates. Improvements to the glass transition temperature (Tg) of aliphatic polycarbonates have been pursued by several groups. We recently showed that attaching a pendant aromatic group to poly(TMC) can enhance the Tg. Also, we have shown that para substituents on the pendant group have an impact on the Tg. Here, we have explored the role of bulky pendant groups and the effect of substituent position on the pendant aromatic ring. We prepared novel naphthalene‐derived poly(TMC)s as well as 2‐Br‐substituted poly(PhTMC). The 2‐bromophenyl derivative showed a Tg of 69.5 °C which represents a nominal increase in comparison to the 4‐bromo derivative that we reported earlier. This suggests that the position of the substituent does not have a critical impact on Tg. With naphthalene derivatives, the increase in steric bulk led to an increase in Tg. Increase of chain length beyond fifty monomer units had a minimal impact on Tg. Finally, when 4‐bromonaphthyl moiety was the pendant group, we observed a Tg of 97 °C. This demonstrates that Tg can be varied significantly by modifying the pendant groups. We have also shown that the 1,3‐diols used in our polymer are non‐cytotoxic.

Substituent Positioning Effects on the Magnetic Properties of Sandwich-Type Erbium(III) Complexes with Bis(trimethylsilyl)-Substituted Cyclooctatetraenyl Ligands.

Lanthanide complexes with judiciously designed ligands have been extensively studied for their potential applications as single-molecule magnets. With the influence of ligands on their magnetic properties generally established, recent research has unearthed certain effects inherent to site differentiation due to the different types and varying numbers of substituents on the same ligand platform. Using two new sandwich-type Er(III) complexes with cyclooctatetraenyl (COT) ligands featuring two differently positioned trimethylsilyl (TMS) substituents, namely, [Li(DME)Er(COT1,5-TMS2)2]n (Er1) and [Na(DME)3][Er(COT1,3-TMS2)2] (Er2) [COT1,3-TMS2 and COT1,5-TMS2 donate 1,3- and 1,5-bis(trimethylsilyl)-substituted cyclooctatetraenyl ligands, respectively; DME = 1,2-dimethoxyethane], and with reference to previously reported [Li(DME)3][Er(COT1,4-TMS2)2] (A) and [K(DME)2][Er(COT1,4-TMS2)2] (B), any possible substituent position effects have been explored for the first time. The rearrangement of the TMS substituents from the starting COT1,4-TMS2 to COT1,3-TMS2 and COT1,5-TMS2, by way of formal migration of the TMS group, was thermally induced in the case of Er1, while for the formation of Er2, the use of Na+ in the placement of its Li+ and K+ congeners is essential. Both Er1 and Er2 display single-molecule magnetic behaviors with energy barriers of 170(3) and 172(6) K, respectively. Magnetic hysteresis loops, butterfly-shaped for Er1 and wide open for Er2, were observed up to 12 K for Er1 and 13 K for Er2. Studies of magnetic dynamics reveal the different pathways for relaxation of magnetization below 10 K, mainly by the Raman process for Er1 and by quantum tunneling of magnetization for Er2, leading to the order of magnitude difference in magnetic relaxation times and sharply different magnetic hysteresis loops.

The effect of substituent position and solvent on thermal Z‒E isomerization of dihydroquinolylazotetrazole dyes: kinetic, thermodynamic, and spectral approaches.

Kinetic and thermodynamic parameters have been investigated for the thermal Z‒E isomerization of dihydroquinolylazotetrazole dyes with alkyl substituents (Me, t-Bu, and Adm) at positions 1 (dyes 2) and 2 (dyes 3) of the tetrazole moiety in two solvents of different polarity, acetonitrile (MeCN) and toluene. The experimental results show crucial dependence of these parameters on a substituent position in the tetrazole moiety and on a solvent. For dyes 2, Eact and ΔH‡ are lower in MeCN than in toluene that results in a high increase in the lifetimes of the Z isomers: from milliseconds in MeCN to minutes in toluene. For dyes 3, the difference in Eact and ΔH‡ in the two solvents is opposite: Eact and ΔH‡ are by more than 20kJmol-1 higher in MeCN, nevertheless, the rate constants for 3 in toluene are comparable with those in MeCN at the ambient temperature and the difference in the behavior is determined by the value of negative entropy of activation. Quantum-chemical calculations of the thermal Z‒E isomerization show the possibility of the process to occur via crossing from the S0 to the thermally induced T1 state. The contribution of this path is highest for 3 in toluene. The analysis of the absorption spectra demonstrates that for the E isomers, the n‒π* and π‒π* transitions are within the long-wavelength absorption band and their positions relative each other are opposite in the solvents: the n‒π* transition is blue-shifted relative to the π‒π* transition in MeCN and is red-shifted in toluene.

The cooperative effects of ligand substituent positions and solvents on spin crossover in Mn(III) complexes based on hexadentate Schiff-base ligands

Spin crossover (SCO), as a molecular bistable phenomenon, has attracted extensive interest. In this paper, the syntheses, crystal structures and magnetic properties of three Mn(III) hexadentate Schiff-base complexes [Mn(3-OMe-sal-N-1,5,8,12)]AsF6·H2O (1), [Mn(4-OMe-sal-N-1,5,8,12)]AsF6·H2O (2) and [Mn(5-OMe-sal-N-1,5,8,12)]AsF6(3) have been reported. The substituent positions of ligands and solvent molecules have a cooperative effect on SCO behavior. Complex 1 shows a complete SCO between the high-spin (HS, S = 2) and low-spin (LS, S = 1) states without thermal hysteresis, and complex 2 shows a gradual incomplete SCO behavior. The transition temperatures of 2 (T1/2 = 241 K) is 98 K higher than that of 1 (T1/2 = 143 K), which indicates that the ligand field strength of (4-OMe-sal-N-1,5,8,12)2– is stronger than that of (3-OMe-sal-N-1,5,8,12)2–. Due to the absence of crystallizing solvent water molecule, complex 3 maintains a HS state in the test temperature range.

Tuning 2D Perovskite Passivation: Impact of Electronic and Steric Effects on the Performance of 3D/2D Perovskite Solar Cells

AbstractSurface passivation with 2D perovskites is a powerful strategy to achieve improved stability and performance in perovskite solar cells (PSCs). Various large organic cations have been successfully implemented, led by phenylethylammonium (PEA+) and its derivatives. However, systematic studies on large sets of cations to understand the effect of substituent position on 2D perovskite passivation and device performance are lacking. Herein, a collection of halogenated PEA+ iodide salts (x‐XPEAI where x: ortho (o), meta (m), para (p), X: F, Cl, Br) are synthesized by a facile method and deposited on top of 3D perovskite. The 2D perovskite layer formation is confirmed by X‐ray diffraction (XRD) and grazing‐incidence wide‐angle X‐ray scattering analyses for all cations, regardless of the nature and position of the halogen. Density functional theory analysis reveals that lower formation energies and higher interfacial dipoles achieved by m‐substituted cations are responsible for enhanced performance compared to their o‐ and p‐ counterparts. While the m‐BrPEAI‐treated device shows a champion efficiency of 23.42%, (VOC=1.13 V, FF=81.2%), considering average efficiencies, stability, and reproducibility, the treatment with m‐ClPEAI salt yields the best overall performance. This comprehensive study provides guidelines for understanding the influence of large cation modification on performance and stability of 3D/2D PSCs.

Quest for a Rational Molecular Design of Alkyl-Distyrylbenzene Liquid by Substitution Pattern Modulation.

Alkyl-π functional molecular liquids (FMLs) are of interest for fabricating soft electronic devices due to their fluidic nature and innate optoelectronic functions from the π-conjugated moiety. However, predictable development of alkyl-π FMLs with the desired liquid and optoelectronic properties is challenging. A series of alkyl-distyrylbenzene (DSB) liquids was studied in terms of the substituent position effect by attaching 2-octyldodecyl chains at (2,4-), (2,5-), (2,6-), and (3,5-). The effect of the alkyl chain length was investigated by attaching 2-hexyldecyl, 2-decyltetradecyl (C10 C14 ), and 2-dodecylhexadecyl at the (2,5-) substituent position. The 2,5-C10 C14 substituent pattern constructed a superior alkyl-DSB liquid with a lower viscosity, intrinsic optical properties, and high thermal- and photo-stabilities. The discovered 2,5-C10 C14 was applied to dicyanostyrylbenzene and comparable liquid physical and optical superiorities were confirmed. This molecular design is useful for creating alkyl-π FMLs with the aforementioned advantages, which are applicable for deformable and flowable optoelectronic devices.

The effect of phthalocyanine's periphery on the biological activities of carbazole-containing metal phthalocyanines.

This study reports the synthesis and characterization of two new mono- and di-substituted phthalonitriles namely 4-((9H-carbazol-3-yl)oxy)-5-chlorophthalonitrile and 4,5-bis((9H-carbazol-3-yl)oxy)phthalonitrile, respectively. Cyclotetramerization of the new phthalonitriles in the presence of zinc(II) acetate resulted in related zinc(II) phthalocyanines. To study the effect of the position and number of substituents on the biological properties of the phthalocyanines, peripherally or non-peripherally tetra-substituted zinc(II) phthalocyanines bearing (9H-carbazol-3-yl)oxy groups, as well as axially di-substituted silicon phthalocyanines containing the same groups, were prepared. Since gold nanoparticles are well-known as efficient drug delivery agents, the surface of these metal nanoparticles was functionalized with all the compounds. This modification also improved the solubility of the phthalocyanines in aqueous media. In this study, the antioxidant, DNA cleavage, and toxic/phototoxic activities of the resultant nanoconjugates were examined. With a combination of metal ion and substituent (nature, number, and position) effects, the silicon(IV) phthalocyanine exhibited the highest biological properties.

Primary- and secondary-sphere effects of amine substituent position on rhenium bipyridine electrocatalysts for CO2 reduction

It is well-established that electrocatalysts with biologically inspired moieties provide advantageous qualities for the efficient transformation of fossil fuel combustion products, such as carbon dioxide, into value-added products. Herein, we present a family of Re(bpy)(CO)3Cl electrocatalysts with pendant NH2 groups in the 4,4′-, 5,5′-, and 6,6′-positions of the bipyridine backbone with the objective of determining the effects of combined primary- and secondary-sphere interactions on the reduction of CO2 to CO. Cyclic voltammetry studies under CO2 indicate that the catalytic onset potential is more positive for 6,6′-NH2-Re, indicating that proximity of the available pendant protons to the metal center is beneficial during catalysis. Controlled potential electrolysis studies demonstrate that, similar to 6,6′-NH2-Re, 4,4′-NH2-Re displays a dependence of Faradaic efficiency (FE) on catalytic potential, reaching a maximum FECO of 91% at −2.40 V. This FE is greater than that observed for 6,6′-NH2-Re but occurs at a more negative potential. Density functional theory (DFT) calculations were performed to compare the HOMO-LUMO gap of these complexes, and the following trend of 4,4′-NH2-Re > 6,6′-NH2-Re > 5,5′-NH2-Re was determined. Mulliken electron population analysis indicates a greater degree of electron density on the metal center for 6,6′-NH2-Re compared to its related congeners, in agreement with the electrolysis studies which illustrate a more favorable CO2 reduction for 6,6′-NH2-Re. Ultimately, it is important that the various catalytic parameters are properly balanced to provide the greatest overall catalytic activity.

Substitution effect on solid parking motif and luminescence of diphenylfuro[2,3-b]quinoxaline isomers

The organic molecules combining light-emitting and charge-transporting property are highly expected. We designed and synthesized a pair of isomers, 2,6-diphenylfuro[2,3-b]quinoxaline (26dPFQ) and 2,7-diphenylfuro[2,3-b]quinoxaline (27dPFQ), and investigated effect of changing substituent position on molecule packing motif, conducting and luminescence feature of resulting materials. In CH2Cl2 solution, both isomers, 26dPFQ and 27dPFQ, emit deep blue light with a wavelength of 422 nm and shows photoluminance quantum yield (PLQY) of 58.9% and 48.7%, respectively. In crystal, the 26dPFQ employs H-type packing motif and retains blue florescent emission with low PLQY (10.0%) while 27dPFQ adopts J-aggregated packing motif and shows enhanced green fluorescent emission with a PLQY of 55.0%. The organic light-emitting devices for both emitters show deep blue emission, the EL peak at 410 nm for 26dPFQ and 424 nm for 27dPFQ, and respectively presents the maximum EQE of 1.2% and 1.0%. The 26dPFQ shows better charge transport capability over 27dPFQ. Our results suggested 2,6-substitution on furo[2,3-b]quinoxaline core are expected to afford such dual functional materials.

Exploring the effect of nitrile substituent position on fluorescence quantum yield of ESIPT-based oxazoline derivatives: A TDDFT investigation

We explore the mechanism specifically on quantum yields difference of 2-(4,4-Dimethyl-4,5-dihydrooxazol-2-yl)-3-hydroxybenzonitrile (1-CN) and 4-(4,4-Dimethyl-4,5-dihydrooxazol-2-yl)-3-hydroxybenzonitrile (3-CN) by density functional theory and time-dependent density functional theory within the Tamm-Dancoff approximation. The structures optimization and the potential energy curves scanning of singlet excited state directly prove that the excited state intramolecular proton transfer (ESIPT) can take place in 1-CN and 3-CN molecules. The calculated spectra show that the fluorescence peaks of two molecules come from the emission of keto* configuration. The non-covalent interaction and the atomic dipole moment corrected Hirshfeld charge are also analyzed. Through the comparison of emission oscillator strength between 1-CN and 3-CN molecules suggests that the radiative transition process is not the main reason for the difference on quantum yields. Internal conversion process is also excluded on account of the large energy gap between S0 and S1. Considering the interaction between singlet and triplet states, both molecules can undergo intersystem crossing. The prominent difference is that, compared with 3-CN, the larger spin-orbit coupling constant and smaller energy level difference promote the intersystem crossing process of 1-CN. This provides direct evidence for the fluorescence quantum yield of 1-CN is lower than that of 3-CN. We envision that the present work can provide help for the synthesis and application of ESIPT compounds with high quantum yields.

Near-Infrared multifunctional theranostic agent with Wave-Like aggregates modulated by substituent position effect

Precise design of organic photosensitizers (PSs) promoted the technological innovation for multimodal imaging-guided synergistic therapy. Nonetheless, various group substitution could not only optimize the basic photophysical behavior, but possibly change the aggregate, which handicaps the deep understanding of the “Formula-Aggergete-Property” relationship. Bearing this in mind, herein two isomers, named 6-TDE and 7-TDE, were prepared via substituting position modification. Among them, 6-TDE exhibited the grid-like structure, while 7-TDE presented wavy-like structure. Despite the aggregates were different, 6-TDE and 7-TDE shared common features including partly twisted backbone and non-overlapped-orbit, hence resulting in similar optical physical behavior such as decent extinction coefficient, near-IR emission, large stockes shifts, etc. Meanwhile, though two PSs could both generated Type-I and Type-II ROS, 7-TDE possessed smaller singlet–triplet splitting (ΔEST), which exhibited favorable ROS as well as outstanding mitochondrial targeting, achieving efficient photodynamic therapy (PDT) effect. During this process, mitochondrial autophagy could be tracked and observed effectively and in real-time. Moreover, 7-TDE presented outstanding performance in multimodal imaging, including fluorescence imaging (FLI), photoacousticimaging (PAI) and photothermal imaging (PTI). This study enriches the strategy of precise molecular engineering to optimize theranostic agents.

Constructing high-performance TADF polymers from non-TADF monomers: a computational investigation.

Thermally activated delayed fluorescence (TADF) polymers excelling in simple, low-cost and large-area solution process ability have attracted tremendous attention recently, but it remains a great challenge for the design of such materials due to the lack of reliable molecular construction guidelines. Here we perform a systematic computational investigation on the construction of TADF polymers from non-TADF monomers to elucidate the effects of polymerization sites, substituent positions and substituent types. The results indicate that the polymerization of 3,6-carbazole-based monomers with different substituents is efficient to build TADF polymers due to their facile π-conjugation extendability. Especially, polymers with para-phenyl-substituted monomers are promising in light of their separated frontier molecular orbitals for small ΔEST with favorable energy levels, bipolar charge transport properties and relatively strong absorption/emission intensity, which should be highly attractive for experimental investigations. These findings and insights are important in revealing the structure-property relation of TADF polymers made from non-TADF monomers with important clues for understanding the construction mechanism and molecular design principles of TADF polymers.

Inkable CF3-functionalized benzothiazole/benzimidazole-Ir(III) complexes for efficient bilayer-inkjet-printed OLEDs

The inkjet-printed organic light-emitting diodes (OLEDs) are gradually gaining popularity due to their low cost, free vacuum environment, patterning, and large-area display capability, but inkable phosphors are yet less reported. In order to develop inkable phosphorescent luminescent material, the introduction of the strong electron-withdrawing CF3 in the C^N ligand of iridium(III) [Ir(III)] complexes is a wise choice. Herein, a serials of phosphorescent Ir(III) complexes consisting of 2-phenybenzothiazole/1,2-diphenylbenzimidazole with the introduction of CF3 group at ortho (o)/meta (m)/para (p) position of the phenyl ring abbreviated as (obt)2Ir(acac), (mbt)2Ir(acac), (pbt)2Ir(acac), (obm)2Ir(acac), (mbm)2Ir(acac), (pbm)2Ir(acac), respectively, were designed and synthesized. The substituent effect and position effect of CF3 group based on the Ir(III) complexes were investigated in all aspects. The bilayer-inkjet-printed OLEDs with those phosphors were studied and showed promising electroluminescent performances. Among them, the OLEDs with (obt)2Ir(acac)/(obm)2Ir(acac) emitter exhibited the maximum external quantum efficiency of 3.7%/3.3%. In addition, the vacuum-deposited OLEDs with those Ir(III) phosphors as emitters were further investigated and demonstrated outstanding device performance.

Substituent positions and types for the inhibitory effects of phenolic inhibitors in coal spontaneous combustion

This study is aimed at investigating the effects of substituent positions and types on the activities of phenolic inhibitors for inhibiting coal spontaneous combustion (CSC). To achieve this aim, six phenolic inhibitors with different substituent positions (ortho-, meta- and para-) and types (methyl, ethyl, isopropyl and tert butyl) were selected for testing their inhibitory effects on Xilinhe coal. First, the temperature-programmed oxidation experiment was performed on the raw coal sample and the inhibited coal samples to explore their CO generation volumes and crossing-point temperatures under low-temperature oxidation conditions. Meanwhile, the corresponding inhibition rates, oxygen consumption rates and apparent activation energy values were calculated. Furthermore, the weight loss processes, surface morphologies and active functional group variations of the raw coal sample and the inhibited coal samples were analyzed with the aid of a thermogravimetric analyzer, a scanning electron microscope and a Fourier transform infrared spectrometer. The test results showed that the phenolic inhibitors can not only infilter into coal but also accumulate on coal surface to form an inhibitor layer. Besides, they can inhibit CSC in both physical and chemical ways during low-temperature oxidation of coal, and their inhibitory effects exhibit varying characteristics in different stages. When the temperature is below 120 °C, the physical inhibitory effects of oxygen isolation and water retention dominate. When it exceeds 120 °C, the chemical inhibitory effect of capturing active free radicals in coal plays a dominant role. The types of substituents have a more notable effect on the activities of phenolic inhibitors than the positions of substituents. The inhibitor with smaller substituent steric hindrance and stronger infiltration ability is more capable of inhibiting CSC physically and chemically. Among the inhibitors with different substituent types, m-cresol boasts the optimal inhibitory effect. Its inhibition rate is 84.4% at 170 °C; the oxygen consumption rate is only 1/4 of that of raw coal; the crossing-point temperature is raised by 30.3 °C to 181.7 °C; and the apparent activation energy values are increased by 7.74 kJ/mol, 16.18 kJ/mol and 20.61 kJ/mol in the slow oxidation stage, the accelerated oxidation stage and the intense oxidation stage, respectively.

Assessing the Effects of Substitution and Substituent Position on the Reactivity of Salicylideneaniline Ligands to Coordinate Transition Metal(II) Ions: a DFT Study

The present scientific contribution aims to investigate computationally the effects of substitution and substituent position on the reactivity of a series of salicylideneaniline derivatives ligands containing 13 molecules. Global reactivity parameters such as the EHOMO, ELUMO, gap energy, electronegativity, chemical hardness, chemical softness, electrophilicity index, and molecular electrostatic potential analysis (MESP) have been calculated at DFT/B3LYP/TZP level of theory and then well discussed to give valuable explanations for the effects of substitution and substituent position on the reactivity of the studied ligands.