Charge Transfer Absorption Research Articles

Exploring the therapeutic potential of ruthenium(II)-bis(benzimidazol-2-yl)pyridine complex on MDA-MB-231, HCT-116 and normal L6 cell lines

The in vitro anticancer efficacy and cytotoxicity of the [Ru(bbp)2]2+ complex (bbp = 2,6-bis(benzimidazol-2-yl) pyridine) on human breast cancerous MDA-MB-231, colorectal HCT-116, and normal cell lines were investigated by direct microscopic and MTT assay methods. The synthesised [Ru(bbp)2]2+ complex was characterised by UV–visible, FTIR, 1H NMR, and MALDI-TOF-MS spectroscopic techniques. The complex showed a metal-to-ligand charge transfer (MLCT) absorption peak at 481 nm. The FTIR spectrum of the complex showed absorption bands in the range of 3458–573 cm−1. The 1H NMR chemical shift values resembled those of the bbp ligand. The molecular ion peak (M+) of the [Ru(bbp)2]2+ complex was obtained at m/z 1013.48. The IC50 values of the complex on MDA-MB-231, HCT-116 and normal L6 cell lines were calculated from the percentage cellular viability and are found to be 28.71, 9.06 and 153.82 µM respectively. The morphological changes in the cell lines at various concentrations of the complex were attributed to the generation of reactive oxygen species (ROS). The obtained result revealed that the anticancer activity of the synthesised complex depends on the concentration of the complex. The complex reduced the proportion of viable cells in both malignant cell lines, causing apoptosis. The results suggeseted that the synthesised complex showed good anticancer activity on the MDA-MB-231 and HCT-116 cell lines with low cytotoxicity. Thus, the present investigation paved the way for the development of novel anticancer drugs.

Planar Chiral Charge-Transfer Cyclophanes: Convenient Synthesis, Circularly Polarized Light-Responsive Photothermal Conversion and Supramolecular Chiral Assembly.

We report herein a series of macrocycles in which the densely π-stacked charge-transfer (CT) donor/acceptor with naphthalenediimides (NDIs) or perylene diimide (PDI) as acceptor moiety pairing various donor moieties are locked by covalent bond. The X-ray crystallography of C8BDT-NDI reveals a short intramolecular π-stacking distance around 3.4 Å and the existence of intermolecular donor/acceptor π-stacking (3.7 Å). The intramolecular CT is highly dependent on the electron-donating ability of donor moiety and replacing carbazole (C8KZ) with benzo[1,2-b:4,5-b']dithiophene (C8BDT) or dihydroindolo[3,2-b]indole (C8DN) redshift CT absorption into NIR region. Notably, both C8BDT-NDI and C8DN-NDI demonstrate excellent photothermal performance, which is a result of the active non-radiative pathways. Interestingly, the different molecular symmetry between donor and acceptor moiety in cyclophanes endow C8BDT-NDI and C8DN-NDI with intrinsic planar chirality. The enantiomeric C8BDT-NDI shows chiral selectivity for incident light, i.e., when irradiated by left-circularly polarized light, (R)-C8BDT-NDI is more sensitive and a higher maximum stable temperature is achieved. While, enantiomeric C8DN-NDI pack with different orientations forming M- and P-handedness helix, respectively, demonstrating molecular planar chirality being transferred and amplified through molecular assembly. These results provide insight into the intramolecular charge transfer in enforced D/A π-stacks in which CT interactions and planar chirality would be engineered through structural control.

Electronic and photocatalytic properties of Cu4 cluster-modified Ag/g-C3N4 single-atom catalysts: A hybrid DFT study

Increasing the active sites on the catalyst surface has been a key goal to increase the catalyst efficiency. This paper presents an efficient conversion of solar energy into chemical energy, realized by a Cu4 cluster-assisted single-atom catalyst (Ag-doped g-C3N4). The catalyst enhances charge transfer and light absorption, and the unique advantages of this approach in the field of photocatalysis are substantiated by density functional theory. Under the synergistic effect of Cu4 clusters, the electronic state density distribution of the Ag single-atom catalyst substrate is drastically altered, which realizes the increase of substrate active sites and rapid charge separation and transfer. Compared with the pristine substrate g-C3N4, the new electronic state distribution and the generation of impurity energy levels lead to the narrowing of the band gap from 2.77 to 1.83 eV, accelerating the transfer and separation of electrons and holes, and enlarging the visible light absorption range from 410 to 760 nm, thus improving the solar energy utilization. Despite the reduced band gap, the conduction and valance band edges of (Ag, Cu4) codoped g-C3N4 still have sufficient potential to split water. Therefore, to improve the photocatalytic performance under visible light, simultaneous codoping of the Ag single atom and Cu4 cluster on g-C3N4 is an effective strategy. The study provides theoretical support for further optimization of single-atom catalysts.

Planar Chiral Charge‐Transfer Cyclophanes: Convenient Synthesis, Circularly Polarized Light‐Responsive Photothermal Conversion and Supramolecular Chiral Assembly

We report herein a series of macrocycles in which the densely π‐stacked charge‐transfer (CT) donor/acceptor with naphthalenediimides (NDIs) or perylene diimide (PDI) as acceptor moiety pairing various donor moieties are locked by covalent bond. The X‐ray crystallography of C8BDT‐NDI reveals a short intramolecular π‐stacking distance around 3.4 Å and the existence of intermolecular donor/acceptor π‐stacking (3.7 Å). The intramolecular CT is highly dependent on the electron‐donating ability of donor moiety and replacing carbazole (C8KZ) with benzo[1,2‐b:4,5‐b']dithiophene (C8BDT) or dihydroindolo[3,2‐b]indole (C8DN) redshift CT absorption into NIR region. Notably, both C8BDT‐NDI and C8DN‐NDI demonstrate excellent photothermal performance, which is a result of the active non‐radiative pathways. Interestingly, the different molecular symmetry between donor and acceptor moiety endows C8BDT‐NDI and C8DN‐NDI with intrinsic planar chirality. The enantiomeric C8BDT‐NDI shows chiral selectivity for incident light, i.e., when irradiated by left‐circularly polarized light, (R)‐C8BDT‐NDI is more sensitive and a higher maximum stable temperature is achieved. While, enantiomeric C8DN‐NDI pack with different orientations forming M‐ and P‐handedness helix, respectively, demonstrating molecular planar chirality being transferred and amplified through molecular assembly. These results provide insight into the intramolecular charge transfer in enforced D/A π‐stacks in which CT interactions and planar chirality would be engineered through structural control.

The PDINH decorated NH2-UiO-67 MOF for promoted photocatalytic Cr(VI) reduction: Performance, and mechanism

A series of composite materials comprising NH₂-UiO-67 metal-organic framework (MOF) and highly π-conjugated 3,4,9,10-perylenetetracarboxylic diimide (PDINH) was synthesized via a facile ball-milling process. These hetero-conjugated MOFs, denoted as PNU-67(X) with varying amounts of PDINH (X = 0.5 %, 1 %, 2 %, and 3 % wt), were evaluated for their photoreduction of Cr(VI) to Cr(III) under visible light irradiation. Systematic investigations revealed a direct correlation between increasing PDINH content and enhancing the conductivity of the MOFs. Additionally, the incorporation of PDINH motifs significantly improved CO₂ capture capability by increasing charge transfer, charge separation, and light absorption. To elucidate the impact of various factors on the photocatalytic performance of PNU-67(3) in Cr(VI) remediation, a comprehensive study was conducted. These factors included pH, initial Cr(VI) concentration, catalyst dosage, scavengers, and scavenger concentration. Notably, PNU-67(3) (5 mg/L) demonstrated 100 % photoreduction efficiency within 35 min, highlighting its potential application in catalyst loading and efficiency compared to other reported UiO-type MOFs. Furthermore, the composites exhibited exceptional stability and reproducibility throughout multiple experimental cycles. Overall, this research presents a promising avenue for constructing heterojunction photocatalysts by integrating MOFs and organic PDINH molecules, offering a viable solution for wastewater remediation.

Synthesis, Structure, and Properties of Nontrivial Iridium(III) Complexes Based on Anthracene-Decorated Benzimidazole Ligand.

Reactions of iridium trichloride hydrate with bulky 2-(9-anthracenyl)-1-phenyl-benzimidazole (anbi) in the presence of N-donor ligands afforded a number of unique noncyclometalated complexes, while attempts to prepare a common μ-chloro-bridged bis-cyclometalated dimer systematically gave a monocyclometalated complex cis-[Ir(C,N-anbi)(N-anbi)Cl2] instead. The obtained complexes were characterized by 1H NMR, high-resolution mass spectrometry, single-crystal and powder X-ray diffraction, UV-vis spectroscopy, and cyclic voltammetry. The noncyclometalated complexes fac-[Ir(N-anbi)(N^N)Cl3)], where N^N are 4,4'-disubstituted 2,2'-bipyridines, are octahedral and contain the anthracene and 2,2'-bipyridine units in a close cofacial arrangement. These complexes were found to be exceptionally inert to the chloride ligand exchange even in the presence of silver triflate, forming a rare trinuclear Ir-μ-Cl3-Ag-μ-Cl3-Ir structure instead. In the monocyclometalated complex, the Ir(III) ion is pentacoordinated in a rare square-pyramidal geometry, where the bulky anthracene fragment is involved in the steric shielding of the metal center. This is in line with the results of gas-phase density functional theory calculations, demonstrating that the experimentally observed structure is energetically most preferable. The monocyclometalated complex is deeply colored due to intense charge-transfer absorption bands in the range 450-650 nm with ε = 2000-5000 M-1 cm-1, superior to the noncyclometalated complexes. The synthesis, structures, and properties of the new complexes are discussed in the context of the related mono-, bis-, and noncyclometalated iridium(III) compounds.

Tunable Interlayer Interactions in Exfoliated 2D van der Waals Framework Fe(SCN)2(Pyrazine)2.

2D materials can be isolated as monolayer sheets when interlayer interactions involve weak van der Waals forces. These atomically thin structures enable novel topological physics and open chemical questions of how to tune the structure and properties of the sheets while maintaining them as isolated monolayers. Here, this work investigates 2D electroactive sheets that exfoliate in solution into colloidal nanosheets, but aggregate upon oxidation, giving rise to tunable interlayer charge transfer absorption and photoluminescence. This optical behavior resembles interlayer excitons, now intensely studied due to their long-lived emission, but which remain difficult to tune through synthetic chemistry. Instead, the interlayer excitons of these framework sheets can be modulated through control of solvent, electrolyte, oxidation state, and the composition of the framework building blocks. Compared to other 2D materials, these framework sheets display the largest known interlayer binding strengths, attributable to specific orbital interactions between the sheets, and among the longest interlayer exciton lifetimes. Taken together, this study provides a microscopic basis for manipulating long-range opto-electronic behavior in van der Waals materials through molecular synthetic chemistry.

Pd Nanoparticle-Modified BiOBr/CdS S-Scheme Photocatalyst for Enhanced Conversion of CO2.

S-scheme heterojunction photocatalyst-coupled plasma-resonance effect can enhance the response range and absorption of light and charge transfer, and, at the same time, obtain strong redox ability, which is an effective way to improve CO2 conversion. In this work, plasma S-scheme heterojunctions of Pd/BiOBr/CdS with heterogeneous interfaces have been successfully constructed by a simple hydrothermal method. The possible reaction mechanism was proposed by in situ infrared, ultraviolet-visible spectroscopy (UV-vis), electron paramagnetic resonance (ESR), density functional theory (DFT), and electrochemical techniques. It was proved that the plasma S-scheme heterojunction can enhance the charge separation efficiency and improve the photocatalytic activity. When the loading ratio is Pd0.6-10%-BiOBr/CdS, it has the best performance, and the CO yield is 30.24 μmol/g, which is 15 and 30 times that of pure BiOBr and CdS, respectively. The results show that with the strong absorption of photon energy and the special electron transfer mode of S-scheme heterojunction, the charge can be effectively separated and transferred, and the photocatalytic activity is significantly improved. This study provides a useful strategy for charge transfer kinetics of plasma S-scheme heterojunction photocatalysts.

Tuning the optical, electrical, structural and photocatalytic activities of mixed metal ferrite by hydrothermal synthesis and polypyrrole reinforcement

This work describes the synthesis, characterization, and photocatalytic evaluation of a polypyrrole-reinforced zinc-nickel mixed metal ferrite (PPy@ Zn0.5Ni0.5Fe2O4) nanohybrid. A facile hydrothermal process is employed to synthesize the nanostructured zinc-nickel mixed metal ferrite (ZNF), and in situ oxidative polymerization is utilized to create the PPy nanohybrid. In this nanohybrid, PPy plays multiple roles: preventing charge recombination, reducing photocorrosion, mitigating particle aggregation in ZNF, and enhancing charge transfer and visible light absorption. The combined electron-capturing ability, intrinsic conductivity, and extensive π-conjugation of PPy, along with the magnetic nature of ZNF, render the PPy@ZNF catalyst highly efficient. The results of photoluminescence, impedance, and UV/Vis analysis confirm that PPy plays a critical role in enhancing photocatalytic performance by facilitating charge transfer and extending visible-light absorption. In practical environmental applications, the PPy@ZNF nanohybrid demonstrated superior photocatalytic activity compared to ZNF alone, degrading 98.5 % of malachite green dye under W-lamp light within 80 min, with a rate constant of 0.031 min−1. Scavenger and cyclic experiments identified the active species involved in dye degradation and assessed the reusability of the nanohybrid. Extensive testing revealed the optimal conditions for photocatalytic efficiency; the considered variables included light intensity, catalyst dose, dye concentration, temperature, irradiation time, and pH. These findings suggest that the PPy-reinforced ZNF nanohybrid offers cost-effectiveness, magnetic recoverability, structural stability, and high efficacy as a visible light-driven catalyst, making it a promising candidate for diverse environmental remediation applications.

S vacancies and heterojunction modulated MoS2/C@Fe3O4 towards improved full-spectrum photo-Fenton catalysis: Enhanced interfacial charge transfer and NIR absorption

Fe3O4-based core–shell/heterojunction composites exhibit favorable photothermal catalytic performance in environmental remediation, but limited by the weak interface electron transport efficiency and poor near infrared (NIR) absorption capacity. Herein, Sv-MoS2/C@Fe3O4 core–shell composites were prepared for the first time by coating S vacancies-bearing MoS2 (Sv-MoS2) on the surface of carbon-decorated Fe3O4 microspheres (C@Fe3O4) derived from copper slag-based polymer microspheres and was used as photothermal catalyst to activate H2O2 towards chlortethromycin hydrochloride (CTC) elimination from wastewater. By virtue of the synergistic effect of the petal-like Sv-MoS2, carbon-decorated layer and multi light reflection in porous microspheres, Sv-MoS2/C@Fe3O4 exhibited excellent full spectrum absorption and carrier migration efficiency, with catalytic activity of 0.149 min−1 and H2O2 utilization rate of 93.6 %. The degradation rate is 3.9 and 3.1 times of C@Fe3O4 and MoS2/C@Fe3O4 under full light irradiation which can heat the solution from room temperature to 72.4 °C. This excellent catalytic performance is mainly originated from that the S-type heterostructure promotes the charge separation, transfer and redox ability, and enhances catalytic oxidation by regulating electron density of the interfacial carbon and reducing the energy barrier of H2O2 activation through S vacancies. Moreover, the decorated carbon layer can serve as a hot core to provide heat to Sv-MoS2 and enhance the collision chance of photogenerated carriers, thus improving the catalytic performance of Sv-MoS2/C@Fe3O4. This work provides new strategies for constructing heterojunction materials with fast electron transport efficiency and using solar energy for environmental remediation.

Modeling of a Single-Band-Ratiometric Sensor Based on Lattice Positive Thermal Expansion in Eu3+-Activated Halide Perovskite Cs2NaEuCl6.

Recently, single-band ratiometric (SBR) thermometry has emerged as an innovative approach to traditional fluorescence thermometry, overcoming uncertainties associated with emission spectrum overlap or scattering while maintaining high spatial resolution and remote monitoring. This paper presents a novel Cs2NaEuCl6 perovskite prepared through a slow-cooling solution method. Additionally, it proposes a temperature sensor model that relies on the thermal quenching of charge-transfer state absorption. Mechanical studies highlight the role of lattice positive thermal expansion in affecting Eu3+ emission. Conversely, a significant emission enhancement is observed upon excitation corresponding to both the ground state and excited state absorption. The distinct luminescent behavior of this Eu3+-activated halide perovskite model makes it suitable for developing a highly sensitive SBR-type sensor with a relative sensitivity (Sr) exceeding 1.5% K-1 and temperature resolution (𝛿T) below 1 K at room temperature. Furthermore, it demonstrates the thermal stability during multiple heating-cooling cycles. Finally, the practical applicability of the proposed SBR model is demonstrated by employing a self-manufactured film sensor that enables precise real-time temperature detection for electronic components. The work is regarded as a significant stride toward the development of cutting-edge and exquisitely sensitive thermometers based on lanthanide-based halide double perovskites.

Colourful 3-amino-1,8-naphthalimide alkyl-substituted fluorescent derivatives

The optical properties of four 3-amino-1,8-naphthalimide derivatives differing in the degree of substitution at the amino functionality were synthesised and studied by UV–visible absorbance and fluorescence spectroscopy in 1:1 (v/v) methanol/water and methanol. The compounds were structurally characterized by NMR, IR and HRMS. The charge transfer absorbance band was observed to shift to longer wavelength with increasing ethyl substitution. The emission band was also observed to shift to longer wavelengths with a decrease in the emission intensity with increasing ethyl substitution due to the peri effect. Irradiation of dye methanol solutions and in the solid state with a 365 nm UV lamp reveals distinct emission colours for each compound. Significantly larger Stokes shifts are observed in methanol than in mixed aqueous methanol. Quantum chemical calculations at the B3LYP/TZVP level of theory provided insight into the optimized ground state geometry, frontier molecular orbitals levels and solute-solvent dynamics revealing a stronger hydrogen bond between the 3-amino-1,8-naphthalimides and methanol in the lowest S1 excited state. The dyes were tested as fluorescent stains in MCF-7 cancer cells and observed to emit green emission in various organelles.

Mechanical Grinding-Induced Intermolecular Charge Transfer for Near-Infrared Photothermal Conversion.

In this study, charge-transfer-type compounds comprising synthesized naphthalenediimide derivative (H4NDISA) or its Pb-based coordination polymer (Pb-NDISA) and suitable primary or secondary amine organic molecules were prepared by the solvent-free mechanical grinding method. The coloration phenomenon arising from charge transfer during grinding serves as a discriminative tool for distinguishing various organic guest molecules. The porous structure of Pb-NDISA crystals facilitates the infiltration of guest molecules and contributes to the preservation of the intermolecular charge transfer state. Moreover, the intermolecular charge transfer induced by grinding exhibits remarkable stability in an ambient atmosphere, underscoring the pivotal role of well-ordered molecules in the mechanical grinding procedure. This mechanochromic phenomenon holds promise for the detection and sensing of organic molecules, while the exceptional charge-transfer absorption characteristics offer the potential for efficient near-infrared photothermal conversion.

Exploring solvatochromism: a comprehensive analysis of research data of the solvent -solute interactions of 4-nitro-2-cyano-azo benzene-meta toluidine

This study investigates the solvatochromic behavior of a new D1 disperse dye, focusing on the 4-nitro-2-cyano-azo-Benzene-metaToluidine type. Using UV-visible spectroscopy, we analyze the dye’s performance in single solvents and binary mixtures. Our analysis includes the evaluation of solvent polarity parameters and dye structure parameters, with emphasis on the longest wavelength intramolecular charge transfer absorption band. We identify nonlinear and linear patterns in the electronic transition energies plots with respect to solvent composition. Statistical analysis considers correlation coefficients, root mean squared error, mean absolute percentage error, and other parameters, providing insights into data accuracy and precision. This experimental and statistical study explores the absorption spectrum, wavelength characteristics, absorption energy, and polarity of a novel azo dye across various solvent and solute environments. These findings contribute to a comprehensive understanding of the dye’s photophysical and photochemical properties, potentially enabling applications in optical sensors and advanced materials.Graphical abstract

Photon energy loss in ternary polymer solar cells based on nonfullerene acceptor as a third component

AbstractUnderstanding photon energy loss caused by the charge recombination in ternary blend polymer solar cells based on nonfullerene acceptors (NFAs) is crucial for achieving further improvements in their device performance. In such a ternary system, however, the two types of donor/acceptor interface coexist, making it more difficult to analyze the photon energy loss. Here, we have focused on the origin of the voltage loss behind a high open‐circuit voltage (VOC) in ternary blend devices based on one donor polymer (poly(2,5‐bis(3‐(2‐butyloctyl)thiophen‐2‐yl)‐thiazolo[5,4‐d]thiazole) [PTzBT]) and two acceptors, including a fullerene derivative ([6,6]‐phenyl‐C61‐butyric acid methyl ester [PCBM]) and an NFA ((2,2′‐((2Z,2′Z)‐(((4,4,9,9‐tetrakis(4‐hexylphenyl)‐4,9‐dihydro‐sindaceno[1,2‐b:5,6‐b′]dithiophene‐2,7‐diyl)bis(4‐((2‐ethylhexyl)oxy)thiophene‐5,2‐diyl))bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile) [IEICO‐4F]), which exhibit VOC similar to that of fullerene‐based PTzBT/PCBM binary devices. From the temperature‐dependent VOC, we found that the effective interfacial bandgap is the same between them: the PTzBT/PCBM/IEICO‐4F ternary blend device is the same as the PTzBT/PCBM fullerene‐based binary device rather than the PTzBT/IEICO‐4F nonfullerene‐based binary device. This means that the recombination center of the ternary blend device is still the interface of PTzBT/PCBM regardless of the incorporation of a small amount of NFA. On the basis of detailed balance theory, we found that the radiative and nonradiative recombination voltage losses for PTzBT/PCBM/IEICO‐4F ternary devices significantly reduced compared to those of fullerene‐based PTzBT/PCBM binary counterparts. This is ascribed to the disappearance of charge transfer absorption due to overlap with the absorption of NFA and the reduction of energetic disorder due to the incorporation of NFA. Through this study, the role of NFAs in voltage loss is once again emphasized, and a ternary system capable of achieving high VOC resulting from significantly reduced voltage loss in ternary blend solar cells is proposed. Therefore, we believe that this research proposes the guidelines that can further enhance the power conversion efficiency of polymer solar cells.

Charge Transfer and Intersystem Crossing in Compact Naphthalenediimide-Phenothiazine Triads: Synthesis and Study of the Photophysical Property with Transient Optical and Electron Paramagnetic Resonance Spectroscopic Methods.

In order to obtain a long-lived charge separation (CS) state in compact electron donor-acceptor molecular systems, we prepared a series of naphthalenediimide (NDI)-phenothiazine (PTZ) triads, with phenylene as the linker between the donor and acceptor. Conformation restriction is imposed to control the mutual orientation of the NDI and PTZ units by attaching methyl groups on the phenylene linker to tune the electronic coupling between the donor and the acceptor. Moreover, the PTZ moiety was oxidized to sulfoxide to tune the ordering of the CS state and the 3LE state (LE: locally excited state). UV-vis absorption spectra indicate electronic coupling between NDI with the phenylene linker as well as the PTZ units, manifested by the appearance of a charge-transfer (CT) absorption band, whereas this coupling is devoid in the triads with conformation restriction imposed. Fluorescence is strongly quenched in the triads compared to the reference compound, indicating electron transfer upon photoexcitation. Femtosecond transient absorption spectra indicate that the CS takes 0.8 ps, and then the 3LE state is formed by charge recombination in 83 ps. Nanosecond transient absorption (ns-TA) spectra show that the 3NDI state was observed in nonpolar solvents such as cyclohexane (triplet state lifetime: 95.7 μs), whereas the CS state was observed in more polar solvents. The CS state lifetimes are up to 1.2 μs (in toluene). Time-resolved electron paramagnetic resonance spectra of the triads in toluene consist of two types of signals: CS states (narrower signals, ∼10 mT) and 3LE states (broader signals, ∼50 to 200 mT). In the spectra of the triads containing PTZ, the CS state signals dominate, whereas for the triads containing oxidized PTZ, the 3NDI signals (zero-field splitting D ≈ 2000 MHz) prevail, both observations being in agreement with the ns-TA spectral studies. The electron spin polarization phase pattern of the 3NDI states of the triads indicates that the intersystem crossing (ISC) mechanism is spin-orbit charge-transfer ISC. Considering the 3CS state as ion pairs, the electron-exchange energy (J) is determined to be -39 to -59 MHz, and the electron spin dipolar interaction is 83-92 MHz.

Beyond the First Coordination Sphere─Manipulating the Excited-State Landscape in Iron(II) Chromophores with Protons.

Molecular transition metal chromophores play a central role in light harvesting and energy conversion. Recently, earth-abundant transition-metal-based chromophores have begun to challenge the dominance of platinum group metal complexes in this area. However, the development of new chromophores with optimized photophysical properties is still limited by a lack of synthetic methods, especially with respect to heteroleptic complexes with functional ligands. Here, we demonstrate a facile and efficient method for the combination of strong-field carbenes with the functional 2,2'-bibenzimidazole ligand in a heteroleptic iron(II) chromophore complex. Our approach yields two isomers that differ predominantly in their excited-state lifetimes based on the symmetry of the ligand field. Deprotonation of both isomers leads to a significant red-shift of the metal-to-ligand charge transfer (MLCT) absorption and a shortening of excited-state lifetimes. Femtosecond transient absorption spectroscopy in combination with quantum chemical simulations and resonance Raman spectroscopy reveals the complex relationship between protonation and photophysical properties. Protonation is found to tip the balance between MLCT and metal-centered (MC) excited states in favor of the former. This study showcases the first example of fine-tuning of the excited-state landscape in an iron(II) chromophore through second-sphere manipulations and provides a new perspective to the challenge of excited-state optimizations in 3d transition metal chromophores.

Interface-regulated S-type core–shell PCN-224@TiO2 heterojunction for visible-light-driven generation of singlet oxygen for selective photooxidation of 2-chloroethyl ethyl sulfide

Selective oxidation of sulfur mustard gas (HD) to non-toxic sulfoxide by the visible-light-catalyzed generation of singlet oxygen (1O2) is a promising degradation strategy. Although PCN-224 can absorb visible light, it suffers from rapid electron-hole recombination and low redox capacity, which limits the performance of HD degradation. Titanium dioxide (TiO2) is an excellent photocatalyst but it lacks visible-light-activity in degrading HD. In this study, PCN-224@TiO2 heterojunction with S-type core–shell structure was synthesized by in-situ growth method to prolong the visible light absorption capacity of TiO2 and inhibit the rapid recombination of PCN-224. The interface formation and internal electric field were optimized by adjusting the Zr/Ti ratio to enhance the charge transfer, redox capacity, electron-hole separation, and visible light absorption. In this study, the formation of heterojunction composites based on Zr-O-Ti linkages is demonstrated by a series of characterization methods. It is demonstrated by experiments and theoretical calculations that PCN-224@TiO2 can generate nearly 100 % 1O2 under visible light conditions without a sacrificial agent, resulting in efficient and selective oxidation of 2-chloroethyl ethyl sulfide (CEES), a simulant of HD, to non-toxic sulfoxide form.

Systematic Modeling of N-Type D–A–D Conjugated Small Molecule-Based Nonfullerene Acceptors for Organic Photovoltaics

This study investigates the impact of six novel (SPZ1–SPZ6) small molecular conjugated nonfullerene acceptors (NFAs), for organic solar cells (OSCs). The designed NFAs are characterized by various advanced quantum chemical simulations of density functional theory (DFT) and time-dependent (TD-DFT) approaches. We revealed in-depth information regarding molecules’ structural-property relationship charge transfer and optical absorption characteristics of designed molecules and compared them with synthetic reference molecules (R). The designed SPZ1–SPZ6 molecules exhibit red-shifted absorption, reduced bandgaps and increased extinction coefficients, indicating improved molecular phase separation during thin-film deposition during device fabrication. Moreover, the modeled SPZ1–SPZ6 molecules significantly enhance photophysical, optoelectronic and photovoltaic parameters compared to R. Among these, the designed small molecule SPZ2 exhibits superior UV–Vis absorption of 730.44 nm, surpassing R and others. SPZ2 features the smallest bandgap (2.00 eV) and has a substantial improvement over R’s 2.37 eV, and this is due to our efficient molecular modeling strategy. Further investigation revealed efficient charge transfer between the SPZ2 acceptor molecule and PTB7-Th donor molecule complex, making this design capable of producing efficient OSCs in the future.

Revealing the Role of Dynamic and Static Disorder on Charge-Transfer-State Absorption in Polymer Solar Cells.

In polymer solar cells (PSCs), charge-transfer (CT) state absorption plays an important role in evaluating the CT-state energy and energy loss. However, due to the disordered nature of polymers, a comprehensive understanding of CT absorption properties remains elusive. Especially, the dominant role of dynamic and static disorder in determining CT absorption is frequently debated. Herein, we theoretically constructed an organic donor-acceptor model to investigate the impact of these two types of disorders on CT absorption properties. It is demonstrated that the CT absorption properties depend significantly on the type of disorder. Specifically, it is found that dynamic disorder has a more significant impact on the peak and position of CT absorption as well as the broadening properties, compared to static disorder. The study indicates that minimizing dynamic disorder can lead to a reduction in overall disorder, which is beneficial for improving the performance of PSCs.