Bond Charge Transfer Research Articles

Thermally Activated Delayed Fluorescence Emitters for Efficient Electrochemiluminescence

AbstractThermally activated delayed fluorescence (TADF) materials have attracted considerable interest due to their ability to enhance electrochemiluminescence (ECL). This is achieved through the efficient upconversion of triplet excitons and the subsequent radiative transitions. However, despite the potential of TADF materials, there have been few studies exploring their application in ECL field. Accordingly, in this concept, a number of TADF materials, which can be categorized into two principal groups based on intramolecular bond charge transfer and intermolecular space charge transfer, are introduced in order to explore the potential for their application in ECL. A brief review of their properties not only helps to deepen the understanding of the nature of TADF materials, but also provides basic guidance and support for the introduction of the TADF mechanism into ECL systems, with the aim of enhancing the luminescence efficiency of ECL.

Charge Transfer Induced Phase Transition in Li2MnO3at High Pressure.

Efficient and better energy storage materials are of utmost technological importance to reduce energy dependence on the fossil fuels. Li2MnO3is one such material having potential to meet most of the requirements for energy storage. This material has been synthesized using solid state synthesis route. High pressure structural and vibrational studies on this material have been carried out upto~ 22 and 26 GPa respectively. These investigations show occurrence of a hitherto unknown second order phase transition to a new low symmetry phase whose symmetry is constrained to be monoclinic with space group P21/n at pressure of ~ 2.3 GPa in Li2MnO3. The bulk modulus and its derivative determined by fitting the P-V data with third order Birch-Murnaghan (B-M) equation of state (EOS) are 113.3 ± 13.1 GPa and 4.1 ± 1.2 respectively. Mode Grüneisen parameter calculated for all the Raman modes show positive values which indicates the absence of any soft mode in this material. A microscopic mechanism based on bond-charge transfer is invoked and applied to understand the spectroscopic changes occurring in this material which also manifests second order structural phase transition. Enhancement in covalent character of Li-O bonds in the Li-O polyhedra is inferred based on the spectroscopic observation and above mechanism.&#xD.

Multiple Energy Transfer Modes From o‐Carborane Dyad Induced by Synergetic Conformational Regulations and Intense Circularly Polarized Luminescence in Self‐Assembly Aggregates

AbstractPhotothermal modulated excited conformations in traditional optoelectronic materials have been extensively investigated for the manipulation of emissive properties. However, photoinduced molecular synergetic conformational changes, which are promising for controlling intramolecular energy transfer modes through molecular orbital breaking, are never been explored. Herein, a novel o‐carborane dyad composed of carbazole units as electron donors and triazine derivatives as electron acceptors is demonstrated to achieve conformation‐dependent emissions and abundant emissions via synergetic conformational changes. Notably, the resulting dyad exhibited multiple conformational changes that induced emissions through different energy transfer modes involved “through space” and “through bond.” Exactly, the electron spin from singlet to triplet state took a flip accompanied by molecular orbitals from π–π molecular orbitals in the space charge transfer style to π and σ molecular orbitals in the bond charge transfer mode. The circularly polarized luminescence (CPL) properties are systematically investigated, exhibiting intense CPL with large glum values. These results provide novel perspectives for elucidating the complicated emission changes in aggregated states, as well as unique perspectives on the relationship between molecular conformations, energy transfer modes, and molecular orbital breaking.

Adsorption and Potential CO Gas-Sensing Performance of the Fe-Doped Ti2CO2-MXenes: A First-Principles Study.

The adsorption behaviors and electronic properties of five gas molecules (CO, H2O, NH3, NO, and C2H6O) on the intrinsic Ti2CO2 and Fe-doped Ti2CO2 were calculated and studied based on first principles. The adsorption height, bond length change, adsorption energy, charge transfer, band structure, differential charge, work function, and recovery time of the two gas adsorption systems were discussed, and their sensing performance was evaluated. The results show that the CO gas molecules have the best adsorption energy and charge transfer on Ti2CO2 modified by the Fe atom (Ti2CO2-Fe). The electrical conductivity obviously increases with the decrease of the band gap, which changes from semiconductor to conductor behavior. The reduction of the work function in the Ti2CO2-Fe system weakens the binding of the electron, which improves the electron flow between the substrate and the gas molecules. In addition, the Ti2CO2-Fe system with H2O molecule participation remained the best adsorption effect on CO gas, and the fast recovery time was 625 s at 398 K. Therefore, Ti2CO2-Fe is a prospective material for the advancement of CO gas-sensitive sensors.

Investigating the potential of monocyclic B9N9 and C18 rings for the electrochemical sensing, and adsorption of carbazole-based anti-cancer drug derivatives: DFT-based first-principle study.

For the first time, the use of monocyclic rings C18 and B9N9 as sensors for the sensing of carbazole-based anti-cancer drugs, such as tetrahydrocarbazole (THC), mukonal (MKN), murrayanine (MRY), and ellipticine (EPT), is described using DFT simulations and computational characterization. The geometries, electronic properties, stability studies, sensitivity, and adsorption capabilities of C18 and B9N9 counterparts towards the selected compounds confirm that the analytes interact through active cavities of the C18 and B9N9 rings of the complexes. Based on the interaction energies, the sensitivity of surfaces towards EPT, MKN, MRY, and THC analytes is observed. The interaction energy of EPT@B9N9, MKN@B9N9, MRY@B9N9, and THC@B9N9 complexes are observed - 20.40, - 19.49, - 20.07, and - 18.27kcal/mol respectively which is more exothermic than EPT@C18, MKN@C18, MRY@C18, and THC@C18 complexes are - 16.37, - 13.97, - 13.96, and - 11.39kcal/mol respectively. According to findings from the quantum theory of atoms in molecules (QTAIM) and the reduced density gradient (RDG), dispersion forces play a significant role in maintaining the stability of these complexes. The electronic properties including FMOs, density of states (DOS), natural bond orbitals (NBO), charge transfer, and absorption studies are carried out. In comparison of B9N9 and C18, the analyte recovery time for C18 is much shorter (9.91 × 10-11 for THC@C18) than that for B9N9 shorter recovery time value of 3.75 × 10-9 for EPT@B9N9. These results suggest that our reported sensors B9N9 and C18 make it faster to detect adsorbed molecules at room temperature. The sensor response is more prominent in B9N9 due to its fine energy gap and high adsorption energy. Consequently, it is possible to think of these monocyclic systems as a potential material for sensor applications.

Ti3C2Tx (T = F, O, OH) as a sensor for dissolved gas in transformer oil: A theoretical study

Power transformer is the hub of power grid energy transmission, and its safe and reliable operation is very important to power grid. In this paper, based on density functional theory, Ti3C2Tx (T = F, O, OH) material was used as sensing material. The adsorption models of Ti3C2Tx and dissolved characteristic gases (H2, CH4, C2H4, C2H6, C2H2, CO, and CO2) in transformer oil are constructed. The adsorption distance, bond length change, adsorption energy, charge transfer and density of states (DOS) of the adsorption system were analyzed. The results showed that the gases can adsorb on the surface of Ti3C2Tx spontaneously. Specifically, CO2, CO, C2H2 and C2H4 exhibit a strong adsorption effect on Ti3C2(OH)2, forming hydrogen bonds or chemical bonds, accompanied by large charge transfer and adsorption energy, indicating Ti3C2(OH)2 shows a good sensing performance for these gases.

Computational investigation on adsorption and activation of atmospheric pollutants CO, NO and SO on small cobalt clusters

The adsorption of CO, NO and SO on cobalt clusters (Co2-7) were investigated using density functional theory. The adsorption energy supports efficient chemisorption of greenhouse gases on the cobalt clusters, with CO and NO forming one to three CoC and CoN bonds, respectively, the first being the most stable. The SO formed bidentate complexes with CoS and CoO bonds in ConSO structures, displaying notably high adsorption energy. The interactions between Con clusters and gas molecules (G) result in weakened bonds of CO, NO, and SO, evident through increased bond lengths, red-shifted frequencies, and lowered local vibrational force constants in ConG complexes. The results with bond weakening and charge transfer from metal to gas molecules suggest strong catalytic potential for small cobalt clusters in activating gas molecules. The current research findings hold significance in the quest for efficient catalytic processes to capture and recycle gaseous pollutants, contributing to a sustainable future.

Adsorption of methotrexate on hyaluronic acid: A comparative DFT and molecular dynamics simulation insights

The potential of hyaluronic acid (HA) as a carrier for methotrexate (MTX) has been explored by quantum mechanics calculations in gaseous and water phases by density functional theory (DFT) and an all-atom molecular dynamics (MD) simulation in an explicit aqueous solvent. MTX adsorption on HA was systematically computed to analyze the bond formation, charge transfer, and binding energies between them in both gaseous and aqueous phases. The DFT analysis revealed polar covalent and electrostatic interactions between HA and MTX in both the gas and water mediums. In addition, according to calculations using natural bond orbitals (NBO), there is a shift of charges from σ and n orbitals in carbon, nitrogen, hydrogen, and oxygen atoms of MTX to n* and σ orbitals in oxygen and hydrogen atoms of HA, with appreciable charge-transfer energies in both the gas and water phases. Due to the solvent effects, the binding energy of the most stable HA-MTX complex was lower in the aqueous phase compared to the gas phase. Subsequently, a MD simulation in the water phase was performed to assess the stability of the complex derived from DFT calculations. The simulation validated the stability of the HA-MTX complex and revealed that MTX is most likely adsorbed onto the top edge of HA via a physical adsorption mechanism. These results indicate that HA may be a viable and efficient carrier for MTX in therapeutic applications.

Chemoselective Vicinal Dichlorination of Alkenes by Iron Ligand-to-Metal Charge-Transfer Catalysis

AbstractWe report the photocatalytic functionalization of terminal alkenes to vicinal dichlorides by using visible light and FeCl3 as a catalyst, LiCl as a chloride source, and air as an oxidant. The transformation is proposed to be initiated by ligand-to-metal charge-transfer bond homolysis of a Fe–Cl bond, giving a highly reactive chloride radical able to initiate the functionalization of olefins. The process shows high chemoselectivity and broad functional-group tolerance with yields of up to 94% under mild conditions.

A weakened Fermi level pinning induced adsorption energy non-charge-transfer mechanism during O2 adsorption in silicene/graphene heterojunctions.

Understanding the mechanisms of gas adsorption on a solid surface and making this process tunable are of great significance in fundamental science and industrial applications. Bond creation and charge transfer are often used to explain the origin of adsorption energy (Ead). However, in this study, a new mechanism is observed in O2 adsorption on pure silicene (PS) and silicene/graphene heterojunction (SGH) surfaces, in which the charge distribution remains almost unchanged, but Ead still has a significant change in the order of 0.3 eV. The weakened Fermi level pinning effect is found to be responsible for this interesting behavior and the variation of Ead is approximately equal to the change of work function. Furthermore, this effect is independent of the twist angles in the van der Waals SGH. Our results are consistent with experimental observations in overcoming the degradation of silicene in air.

Self-indicating polymers: a pathway to intelligent materials.

Self-indicating polymers have emerged as a promising class of smart materials that possess the unique ability to undergo detectable variations in their physical or chemical properties in response to various stimuli. This article presents an overview of the most important mechanisms through which these materials exhibit self-indication, including aggregation, phase transition, covalent and non-covalent bond cleavage, isomerization, charge transfer, and energy transfer. Aggregation is a prevalent mechanism observed in self-indicating polymers, where changes in the degree of molecular organization result in variations in optical or electrical properties. Phase transition-induced self-indication relies on the transformation between different phases, such as liquid-to-solid or crystalline-to-amorphous transitions, leading to observable changes in color or conductivity. Covalent bond cleavage-based self-indicating polymers undergo controlled degradation or fragmentation upon exposure to specific triggers, resulting in noticeable variations in their structural or mechanical properties. Isomerization is another crucial mechanism exploited in self-indicating polymers, where the reversible transformation between the different isomeric forms induces detectable changes in fluorescence or absorption spectra. Charge transfer-based self-indicating polymers rely on the modulation of electron or hole transfer within the polymer backbone, manifesting as changes in electrical conductivity or redox properties. Energy transfer is an essential mechanism utilized by certain self-indicating polymers, where energy transfer between chromophores or fluorophores leads to variations in the emission characteristics. Furthermore, this review article highlights the diverse range of applications for self-indicating polymers. These materials find particular use in sensing and monitoring applications, where their responsive nature enables them to act as sensors for specific analytes, environmental parameters, or mechanical stress. Self-indicating polymers have also been used in the development of smart materials, including stimuli-responsive coatings, drug delivery systems, food sensors, wearable devices, and molecular switches. The unique combination of tunable properties and responsiveness makes self-indicating polymers highly promising for future advancements in the fields of biotechnology, materials science, and electronics.

Structural insight into imidazopyridines and benzimidazoles: the importance of the hydrogen bond, π-stacking interactions and intramolecular charge transfer effect for fluorescence

An investigation of the impact of the N-position, H-bond and π-stacking for fluorescence in imidazopyridine and benzimidazole derivatives.

Coverage-sensitive mechanism of electrochemical NO reduction on the SrTiO3(001) surface: a DFT investigation.

Due to its adverse environmental and human health hazards, addressing the elimination of nitric oxide (NO) has become a pressing concern for modern society. Currently, electrochemical NO reduction provides a new alternative to traditional selective catalytic reduction technology under mild reaction conditions. However, the complexity and variability of products make the coverage of NO an influencing factor that needs to be investigated. Hence, this study delves into the coverage-sensitive mechanism of electrochemical NO reduction on cost-effective perovskite catalysts, using SrTiO3 as an example, through density functional theory calculations. Phase diagrams analysis reveals that the coverage range from 0.25 to 1.00 monolayer (ML) coverage is favorable for NO adsorption. Gibbs free energy results indicate that the selectivity is significantly influenced by NO coverage. NH3 is likely to be generated at low coverage, while N2O and N2 are more likely to be produced at high coverage through a dimer mechanism. Charge analysis suggests that the charge transfer and Ti-O bond strength between reactants and catalysts are crucial factors. This work not only provides deep insights into coverage-sensitive reaction mechanisms but also is a guideline towards further rational design of high-performance perovskite catalysts.

Feeling the strain: Enhancing the electrochemical performance of olivine LiMnPO[formula omitted] as cathode materials for Li-ion batteries through strain effects

Currently, the improvement of Li-ion batteries (LIBs) is more important than ever, especially due to the increasing spread and rapid progress of electric vehicles and high-tech applications. Materials used for positive electrodes are one of the main constituents of batteries, which typically determine their electrochemical efficiency. Phospho-olivine LiMnPO4 (LMP) material has been regarded as a potential positive electrode material for LIBs due to its outstanding properties. However, it suffers from low electronic and ionic conductivity. Therefore, this work aims to overcome these drawbacks by applying a biaxial strain to LMP. In this regard, we used density functional theory calculations to investigate the effect of biaxial strain on the dynamic and thermal stabilities, structural, electronic, ionic diffusion, electrochemical potential, and defect properties of LiMnPO4 (LMP) structure, as well as on the Average (Mn–O, Li–O and P–O) bond lengths, electrical conductivity, and charge transfer. Moreover, the influence of anti-site defects on the ionic conductivity of LMP compound was evaluated. Our findings suggest that the biaxial tensile strain has a remarkable effect on the rate performance of LMP cathode material. A biaxial tensile strain of +2% reduces the band gap of LMP from 3.51 to 3.41 eV, and ameliorates the diffusion coefficient by 100 times. Furthermore, the migration barrier was calculated to be 0.37 eV for strained (+2%) defective MP, lower than 1.12 eV for unstrained defective MP, indicating that biaxial tensile strain can mitigate the negative effect of anti-site defects on Li-ion migration. These results can prompt us to suggest biaxial tensile strain as a good strategy for improving the electrochemical performance of LMP as cathode material for LIBs. Furthermore, this study may supply insights to cathode material designers and engineers on the importance of an appropriate biaxial strain value to improve the rate performance of LiMnPO4 as cathode materials for LIB batteries.

Unraveling the effect of pressure on structural phase transition, electronic, and optical properties of Hf1-xSixO2 (x = 0, 0.03, 0.06, 0.09): A first-principles investigation

The non-centrosymmetric phase of HfO2 with excellent Si compatibility has great importance in integrated photonic circuits, non-volatile memory, and ferroelectric field effect transistors. We report a theoretical study of pressure-induced phase transition from a centrosymmetric m-HfO2 to non-centrosymmetric o-HfO2 with Si doping. The reported phase transition pressures, i.e. 15, 14, 8, and 8 GPa for x = 0, 0.03, 0.06, and 0.09, respectively, for Hf1-xSixO2 are in excellent agreement with available experimental results. With increasing Si concentrations, the transition pressures reduce significantly, which is explained in terms of bond length and charge transfer. The thermal stability of the obtained o-HfO2 phase is examined via ab-initio molecular dynamics up to its synthesis temperature. The negative formation energy also confirms its thermodynamical stability. Density of states indicates the noticeable appearance of Si states in the lower conduction band and an increase in the extent of hybridization between Hf-5d, O-2p, and Si-2p atomic states. The doping changes the nature of band gap from indirect to direct, concurrently reducing the magnitude. The o-HfO2 shows a low value of static dielectric constant, which results in a smaller refractive index (1.82) and lower reflectivity in the infrared and visible regions.

Efficient Intersystem Crossing and Long-lived Charge-Separated State Induced by Through-Space Intramolecular Charge Transfer in a Parallel Geometry Carbazole-Bodipy Dyad.

The design of efficient heavy atom-free triplet photosensitizers (PSs) based on through bond charge transfer (TBCT) features is a formidable challenge due to the criteria of orthogonal donor-acceptor geometry. Herein, we propose using parallel (face-to-face) conformation carbazole-bodipy donor-acceptor dyads (BCZ-1 and BCZ-2) featuring through space intramolecular charge transfer (TSCT) process as efficient triplet PS. Efficient intersystem crossing (ΦΔ =61 %) and long-lived triplet excited state (τT =186 μs) were observed in the TSCT dyad BCZ-1 compared to BCZ-3 (ΦΔ =0.4 %), the dyad involving TBCT, demonstrating the superiority of the TSCT approach over conventional donor-acceptor system. Moreover, the transient absorption study revealed that TSCT dyads have a faster charge separation and slower intersystem crossing process induced by charge recombination compared to TBCT dyad. A long-lived charge-separated state (CSS) was observed in the BCZ-1 (τCSS =24 ns). For the first time, the TSCT dyad was explored for the triplet-triplet annihilation upconversion, and a high upconversion quantum yield of 11 % was observed. Our results demonstrate a new avenue for designing efficient PSs and open up exciting opportunities for future research in this field.

Efficient Intersystem Crossing and Long‐lived Charge‐Separated State Induced by Through‐Space Intramolecular Charge Transfer in a Parallel Geometry Carbazole‐Bodipy Dyad

AbstractThe design of efficient heavy atom‐free triplet photosensitizers (PSs) based on through bond charge transfer (TBCT) features is a formidable challenge due to the criteria of orthogonal donor‐acceptor geometry. Herein, we propose using parallel (face‐to‐face) conformation carbazole‐bodipy donor‐acceptor dyads (BCZ‐1 and BCZ‐2) featuring through space intramolecular charge transfer (TSCT) process as efficient triplet PS. Efficient intersystem crossing (ΦΔ=61 %) and long‐lived triplet excited state (τT=186 μs) were observed in the TSCT dyad BCZ‐1 compared to BCZ‐3 (ΦΔ=0.4 %), the dyad involving TBCT, demonstrating the superiority of the TSCT approach over conventional donor‐acceptor system. Moreover, the transient absorption study revealed that TSCT dyads have a faster charge separation and slower intersystem crossing process induced by charge recombination compared to TBCT dyad. A long‐lived charge‐separated state (CSS) was observed in the BCZ‐1 (τCSS=24 ns). For the first time, the TSCT dyad was explored for the triplet‐triplet annihilation upconversion, and a high upconversion quantum yield of 11 % was observed. Our results demonstrate a new avenue for designing efficient PSs and open up exciting opportunities for future research in this field.

Impact of dielectric constant of solvent on the formation of transition metal-ammine complexes.

The DFT-level computational investigations into Gibbs free energies (ΔG) demonstrate that as the dielectric constant of the solvent increases, the stabilities of [M(NH3 )n ]2+/3+ (n = 4, 6; M = selected 3d transition metals) complexes decrease. However, there is no observed correlation between the stability of the complex and the solvent donor number. Analysis of the charge transfer and Wiberg bond indices indicates a dative-bond character in all the complexes. The solvent effect assessed through solvation energy is determined by the change in the solvent accessible surface area (SASA) and the change in the charge distribution that occurs during complex formation. It has been observed that the SASA and charge transfer are different in the different coordination numbers, resulting in a variation in the solvent effect on complex stability in different solvents. This ultimately leads to a change between the relative stability of complexes with different coordination numbers while increasing the solvent polarity for a few complexes. Moreover, the findings indicate a direct relationship between ΔΔG (∆Gsolvent -∆Ggas ) and ΔEsolv , which enables the computation of ΔG for the compounds in a particular solvent using only ΔGgas and ΔEsolv . This approach is less computationally expensive.

MOF-derived ZnO nanocage decorated with Nd2O3 nanorods for high-performance triethylamine sensing

MOF-derived metal oxides are promising porous materials for gas detection. And neodymium oxide could be favorable for the sensing process due to the active chemistry of lanthanide Nd. Here, a triethylamine sensor based on Nd2O3-ZnO composites was constructed. The gas-sensing properties and mechanism were studied in detail. The XPS and O2-TPD characterization confirmed the increase of chemisorbed oxygen on the composite surface. And the density functional theory calculation results showed that oxygen molecule has stronger chemical adsorption, enhanced charge transfer and longer bond length on the surface of Nd2O3 than that on ZnO. The adsorption and activation for oxygen, the structural advantage and the electronic modulation effect of heterojunction lead to the high performance of the composite for triethylamine detection. The response of the composite to 100 ppm TEA was 15.7 times higher than that of ZnO. Meanwhile, the sensor showed a lower operating temperature and detection limit (150 ppb). This study provides a reference for the construction of high-performance TEA sensors and the application of Nd2O3 in the sensing field.

σ‐Hole intermolecular interactions between carbon oxides and dihalogens: Ab‐initio investigations

Recently, halogen bonding (XB) has received increased attention as a new type of non-covalent interaction widely present in nature. In this work, quantum chemical calculations at DFT level have been carried out to investigate halogen bonding interactions between COn (n= 1 or 2) and dihalogen molecules XY (X=F, Cl, Br, I and Y=Cl, Br, I). Highly accurate all-electron data, estimated by CCSD(T) calculations, were used to benchmark the different levels of computational methods with the objective of finding the best accuracy/computational cost. Molecular electrostatic potential, interaction energy values, charge transfer, UV spectra, and natural bond orbital (NBO) analysis were determined to better understand the nature of the XB interaction. Density of states (DOS) and projected DOS were also computed. Hence, according to these results, the magnitude of the halogen bonding is affected by the halogen polarizability and electronegativity, where for the more polarizable and less electronegative halogen atoms, the σ-hole is bigger. Furthermore, for the halogen-bonded complexes involving CO and XY, the OC∙∙∙XY interaction is stronger than the CO∙∙∙XY interaction. Thus, the results presented here can establish fundamental characteristics of halogen bonding in media, which would be very helpful for applying this noncovalent interaction for the sustainable capture of carbon oxides.