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High permittivity materials are required for efficient organic photovoltaic devices, and the addition of the conjugated polymer composite poly(3,4-ethylenedioxythiophen) polystyrene sulfonate (PEDOT:PSS) to dielectric polymers has been shown to significantly heighten their permittivity. The permittivity of PEDOT:PSS at the optical and microwave frequencies has been investigated, but PEDOT:PSS layers are mainly used for low-frequency device applications, where accurate dielectric property measurements are hindered by their high electrical conductivity and the problems arising from the metal-polymer interfaces. Here, we determine the complex relative permittivity ( ε r * = ε r ′ − j ε r ″ ) of PEDOT:PSS layers perpendicular to the layer plane in the 10−2–106 Hz range by combining data from the reactive energy estimations and electrochemical impedance spectroscopy, and discover that: ε r ′ at <1 Hz is ultra-high (∼106) decreasing with frequency to ∼5 at 106 Hz; the experimental data fit the Cole-Cole dielectric relaxation model by considering multiple relaxation mechanisms; PEDOT:PSS polarizes nonlinearly and ε r ′ increases with the intensity of the applied external field; low frequency ε r ′ increases with both thickness and temperature of the layer, opposite trend of temperature-dependence prevails at >103 Hz; the dielectric properties of PEDOT:PSS are highly anisotropic and the in-plane ε r ′ at 1.0 kHz is three orders of magnitude higher than the vertical ε r ′ ; and that the ε r ′ ′ decreases proportional to the reciprocal of frequency (1/f). The latter finding provides an explanation for the ubiquitous pink noise accompanying signals transmitted through organic conductor links. The described methodology can be adopted for investigations on other conjugated polymers. [ABSTRACT FROM AUTHOR]

The synthesis and properties of a series of 11,11,12,12‐tetracyano‐9,10‐anthraquinodimethane (TCAQ) inspired electron acceptors based on thiophene‐fused quinone and triptycene motifs is presented. This has yielded insights into structure‐property relationships for establishing and modulating simultaneous two‐electron reduction processes in TCAQ analogues. These new compounds were synthesised using a Friedel‐Crafts acylation between triptycene and thiophene‐3,4‐dicarbonyl chloride. Isomeric para‐quinones featuring a [c]‐fused thiophene on one side and a β,β‐ or α,β‐fused triptycene on the other were isolated alongside a thiophene‐3,4‐diketone which bears two triptycene fragments. Knoevenagel condensation of these products with malononitrile produced a quinoidal bis(dicyanomethylene), an oxo‐dicyanomethylene and an acyclic bis(dicyanomethylene). This series of new electron accepting molecules has been studied using X‐ray crystallography and the implications of their 3D structures on NMR and UV/vis absorbance spectroscopy and cyclic voltammetry results have been ascertained with conclusions underpinned by computational methods. [ABSTRACT FROM AUTHOR]

Organic metal complexes (OMCs) transport trace metals (e.g. , Co, Ni, Cu) from surface soils, via the unsaturated zone, to sites of cave carbonate (speleothem) formation. OMCs clearly imprint on speleothem trace element chemistry, but the role of kinetic factors in the signal transfer process has yet to be elucidated. We investigated whether OMCs may viably link metal concentrations in stalagmites and local hydrology (i.e. , drip rate), via their time-sensitive dissociation (or 'decay') in the speleothem water thin-film. We performed competitive ligand exchange experiments using water and soil samples from eight geographically diverse Aotearoa New Zealand caves, providing a first comparative characterisation of speleothem-specific OMC kinetics. Critically, this approach corroborated that NOM ligands limit transition metal availability at the dripwater-speleothem interface, exhibiting stabilities on the order Cu ≈ Co > Ni, whereas organic complexation of the alkaline earth metals Mg and Sr was virtually absent. Systematic variations of OMC stability with natural organic matter characteristics were not observed amongst water samples, whilst enhanced complexation was clearly evident in the comparably organic-rich soil extracts. Our results imply that the supply of transition metals to speleothems is inversely related to drip rate, increasing with drip interval via the decay of OMCs. This process appears most sensitive on time-scales relevant to typical speleothem-forming settings (<0 to ca. 40 drips min−1, corresponding to ca. <5.6 mL min−1), and therefore provides a general, mechanistic link to a quantitative proxy of palaeoclimatic cave drip rates. [ABSTRACT FROM AUTHOR]

In the present study the behavior of Cu(II) and Zn(II) complexes with ethylenediamine and 2,2′:6′,2′′ terpyridine in an aqueous environment was studied by classical MD simulations. Special attention was paid to the effect of Cu2+ for Zn2+ substitution on complex water surroundings and mobility. The replacement of a metal ion affects the structure of the complex water environment only in the vicinity of its location. However, it changes such a characteristic as the lifetime of a water molecule in the first coordination shell of a metal which can significantly affect the mobility of the complex. Moreover, the degree of influence on translational and rotational mobility can be different. [ABSTRACT FROM AUTHOR]

One of the most fascinating aspects of condensed matter is its ability to conduct electricity, which is particularly pronounced in conventional metals such as copper or silver. Such behavior stems from a strong tendency of valence electrons to delocalize in a periodic potential created by ions in the crystal lattice of a given material. In many advanced materials, however, this basic delocalization process of the valence electrons competes with various processes that tend to localize these very same valence electrons, thus driving the insulating behavior. The two such most important processes are the Mott localization, driven by strong correlation effects among the valence electrons, and the Anderson localization, driven by the interaction of the valence electrons with a strong disorder potential. These two localization processes are almost exclusively considered separately from both an experimental and a theoretical standpoint. Here, we offer an overview of our long-standing research on selected organic conductors and manganites, that clearly show the presence of both these localization processes. We discuss these results within existing theories of Mott–Anderson localization and argue that such behavior could be a common feature of many advanced materials. [ABSTRACT FROM AUTHOR]

As a hybrid material, metal organic frameworks (MOFs) contain unique characteristics for biomedical applications such as high porosity, large surface area, different crystalline morphologies, and nanoscale dimensions. These frameworks are assembled through the interconnection of organic linkers with metal nodes, while the engineering of an MOF for biomedical applications requires versatile linkers with acceptable symmetry. Porphyrin, as an organic linker with interesting photochemical and photophysical properties, attracted the attention of many for engineering the potent multifunctional porphyrinic metal organic frameworks (PMOFs). In this regard, a large number of approaches were conducted for designing robust practical PMOFs with a wide range of applications. In this review, we introduced another perspective of MOFs and coordination polymers constructed from porphyrinic linkers with a special focus on those synthesized by meso-tetrakis (4-carboxyphenyl) porphyrin (TCPP). In the following, we summarized and discussed the different types of PMOFs and their biomedical applications in terms of diagnostic agent, therapeutic platform, and drug delivery vehicle. [ABSTRACT FROM AUTHOR]

[Display omitted] • Three zero-dimensional organic metal halides with different emission characteristics were synthesized. • The photophysical properties of the as-synthesized compounds were investigated in detail. • We demonstrated Sb3+-doped compounds in single-component white light illumination latent fingerprint detection. • Based on Sb3+-doped Sn(IV) compounds, a triple-mode reversible PL switch of off-onI-onII-off was achieved under different external stimuli. The host lattice environments of Sb3+ has a great influence on its photophysical properties. Here, we synthesized three zero-dimensional organic metal halides of (TPA) 2 SbCl 5 (1), Sb3+-doped (TPA)SnCl 5 (H 2 O)·2H 2 O (Sb3+-2), and Sb3+-doped (TPA) 2 SnCl 6 (Sb3+-3). Compared with the intense orange emission of 1 , Sb3+-3 has smaller lattice distortion, thus effectively suppressing the exciton transformation from singlet to triplet self-trapped exciton (STE) states, which makes Sb3+-3 has stronger singlet STE emission and further bring a white emission with a photoluminescence quantum efficiency (PLQE) of 93.4%. Conversely, the non-emission can be observed in Sb3+-2 even though it has a similar [SbCl 5 ]2- structure to 1 , which should be due to its indirect bandgap characteristics and the effective non-radiative relaxation caused by H 2 O in the lattice. Interestingly, the non-emission of Sb3+-2 can convert into the bright emission of Sb3+-3 under TPACl DMF solution treatment. Meanwhile, the white emission under 315 nm excitation of Sb3+-3 can change into orange emission upon 365 nm irradiation, and the luminescence can be further quenched by the treatment of HCl. Therefore, a triple-mode reversible luminescence switch of off-onI-onII-off can be achieved. Finally, we demonstrated the applications of Sb3+-doped compounds in single-component white light illumination, latent fingerprint detection, fluorescent anti-counterfeiting, and information encryption. [ABSTRACT FROM AUTHOR]

Organic conductors are a promising material for future electronics. Although, its processing is a big challenge. In this manuscript, we demonstrate micropatterning of polyaniline within the pores of a polycarbonate membrane to fabricate a device for a conductometric sensor. The aqueous dispersion of polyaniline particles was prepared by single pot oxidative polymerization of aniline monomer using dodecylbenzene sulfonic acid as a surfactant as well as a dopant, and the polyaniline from its aqueous dispersion was then precipitated within the pores of polycarbonate membrane by adding solvents of varying polarities. The phase diagram of precipitation was drawn by titrating the polyaniline dispersion with tetrahydrofuran solvent. The dispersion was characterized by Fourier transform infrared spectroscopy and UV-Vis spectroscopy, as well as a transmission electron microscope. The molecular weight of the synthesized polyaniline was measured by gel permission chromatography. The morphology of polyaniline has been compared through transmission electron microscopy in its dispersed form and after precipitation. Field emission scanning electron microscopy was used to see the growth of channel formation of precipitated polyaniline within the pores of the polycarbonate membrane. The electroactivity of the precipitated polyaniline was measured by in-situ conductance measurement as a function of the electrochemical state. Polyaniline dispersion, synthesized by using dodecylbenzene sulfonic acid as a protonic acid as well as a soft template, is precipitated in the pores of the polycarbonate membrane to fabricate a device for a conductometric sensor. The electrochemical measurements revealed that the precipitated polyaniline pattern retains its electroactivity. [ABSTRACT FROM AUTHOR]

This paper details the preparation of an aluminum-based organic metal complex doped with fluorine and nitrogen (2-Ml/Al–F–N). The synthesis method combines hydrothermal synthesis and calcination for modification. The catalyst was thoroughly characterized for its composition, structure, and morphology using various techniques, including XRD, FT-IR, XPS, SEM, TEM, and others. The electrochemical performance of the material was assessed using an electrochemical workstation, and gas chromatography was employed to analyze the results. DFT calculations were used to compute the material's properties and energy barrier diagram. The findings demonstrate that the catalyst exhibits a carbon nanoline morphology and showcases high catalytic activity in the CO2RR to CO. Notably, the catalyst exhibits excellent performance with a maximum current density of 14.08 mA cm−2 and a peak faradaic efficiency of 90.1% at −1.1 V vs. RHE. The active sites are predominantly located within the nanoline structure. The DFT calculations reveal that the introduction of ammonium fluoride during the synthesis process leads to the formation of a highly efficient fluorinated aluminum metal catalytic center derived from nonahydrate aluminum nitrate. This specific structure demonstrates excellent hydrogen suppression properties and effectively lowers desorption energy barriers, which enhances the CO2RR activity and promotes the electrocatalytic reduction of CO2 to CO. [ABSTRACT FROM AUTHOR]

Aldol condensation is a cost‐effective and sustainable synthetic method, offering the advantages of low complexity, substrate universality, and high efficiency. Over the past decade, it has become popular for creating next‐generation organic functional materials, particularly rigid‐rod conjugated (semi)conductors. This review focuses on conjugated small molecules, oligomers, and polymeric (semi)conductors synthesized through aldol condensation, with emphasis on their remarkable features in advancing n‐type organic field‐effect transistors (OFETs), organic electrochemical transistors (OECTs), organic photovoltaics (OPVs), and organic thermoelectrics (OTEs) as well as NIR‐II photothermal conversion. Coherence character, optical properties, microstructure, and chain conformation are investigated to understand material‐property relationships. Future applications and challenges in this area are also discussed. [ABSTRACT FROM AUTHOR]

The construction of low-symmetry topological supramolecular structures using bistable building blocks remains challenging. We report an unusual truncated triangular prismatic cage with D3h symmetry using a ligand with both cis- and trans-configurations upon coordination with metal. This work provides new ideas and methods for the future synthesis of low-symmetry topological supramolecules. [ABSTRACT FROM AUTHOR]

Aldol condensation is a cost‐effective and sustainable synthetic method, offering the advantages of low complexity, substrate universality, and high efficiency. Over the past decade, it has become popular for creating next‐generation organic functional materials, particularly rigid‐rod conjugated (semi)conductors. This review focuses on conjugated small molecules, oligomers, and polymeric (semi)conductors synthesized through aldol condensation, with emphasis on their remarkable features in advancing n‐type organic field‐effect transistors (OFETs), organic electrochemical transistors (OECTs), organic photovoltaics (OPVs), and organic thermoelectrics (OTEs) as well as NIR‐II photothermal conversion. Coherence character, optical properties, microstructure, and chain conformation are investigated to understand material‐property relationships. Future applications and challenges in this area are also discussed. [ABSTRACT FROM AUTHOR]

Physical sensors have emerged as a promising technology for real‐time healthcare monitoring, which tracks various physical signals from the human body. Accurate acquisition of these physical signals from biological tissue requires excellent electrical conductivity and long‐term durability of the sensors under complex mechanical deformation. Conductive polymers, combining the advantages of conventional polymers and organic conductors, are considered ideal conductive materials for healthcare physical sensors due to their intrinsic conductive network, tunable mechanical properties, and easy processing. Doping engineering has been proposed as an effective approach to enhance the sensitivity, lower the detection limit, and widen the operational range of sensors based on conductive polymers. This approach enables the introduction of dopants into conductive polymers to adjust and control the microstructure and energy levels of conductive polymers, thereby optimizing their mechanical and conductivity properties. This review article provides a comprehensive overview of doping engineering methods to improve the physical properties of conductive polymers and highlights their applications in the field of healthcare physical sensors, including temperature sensors, strain sensors, stress sensors, and electrophysiological sensing. Additionally, the challenges and opportunities associated with conductive polymer‐based physical sensors in healthcare monitoring are discussed. [ABSTRACT FROM AUTHOR]

The interaction between excited states of a molecule and excited states of a metal nanostructure (e.g., plasmons) leads to hybrid states with modified optical properties. When plasmon resonance is swept through molecular transition frequency, an avoided crossing may be observed, which is often regarded as a signature of strong coupling between plasmons and molecules. Such strong coupling is expected to be realized when 2|⟨U⟩|/ℏΓ > 1, where ⟨U⟩ and Γ are the molecule–plasmon coupling and the spectral width of the optical transition, respectively. Because both ⟨U⟩ and Γ strongly increase with decreasing distance between a molecule and a plasmonic structure, it is not obvious that this condition can be satisfied for any molecule–metal surface distance. In this work, we investigate the behavior of ⟨U⟩ and Γ for several geometries. Surprisingly, we find that if the only contributions to Γ are lifetime broadenings associated with the radiative and nonradiative relaxation of a single molecular vibronic transition, including effects on molecular radiative and nonradiative lifetimes induced by the metal, the criterion 2|⟨U⟩|/ℏΓ > 1 is easily satisfied by many configurations irrespective of the metal–molecule distance. This implies that the Rabi splitting can be observed in such structures if other sources of broadening are suppressed. Additionally, when the molecule–metal surface distance is varied keeping all other molecular and metal parameters constant, this behavior is mitigated due to the spectral shift associated with the same molecule–plasmon interaction, making the observation of Rabi splitting more challenging. [ABSTRACT FROM AUTHOR]

The achievement of significant photoluminescence (PL) in lanthanide ions (Ln3+) has primarily relied on host sensitization, where energy is transferred from the excited host material to the Ln3+ ions. However, this luminous mechanism involves only one optical antenna, namely the host material, which limits the accessibility of excitation wavelength‐dependent (Ex‐De) PL. Consequently, the wider application of Ln3+ ions in light‐emitting devices is hindered. In this study, we present an organic–inorganic compound, (DMA)4LnCl7 (DMA+=[CH3NH2CH3]+, Ln3+=Ce3+, Tb3+), which serves as an independent host lattice material for efficient Ex‐De emission by doping it with trivalent antimony (Sb3+). The pristine (DMA)4LnCl7 compounds exhibit high luminescence, maintaining the characteristic sharp emission bands of Ln3+ and demonstrating a high PL quantum yield of 90–100 %. Upon Sb3+ doping, the compound exhibits noticeable Ex‐De emission with switchable colors. Through a detailed spectral study, we observe that the prominent energy transfer process observed in traditional host‐sensitized systems is absent in these materials. Instead, they exhibit two independent emission centers from Ln3+ and Sb3+, each displaying distinct features in luminous color and radiative lifetime. These findings open up new possibilities for designing Ex‐De emitters based on Ln3+ ions. [ABSTRACT FROM AUTHOR]

The achievement of significant photoluminescence (PL) in lanthanide ions (Ln3+) has primarily relied on host sensitization, where energy is transferred from the excited host material to the Ln3+ ions. However, this luminous mechanism involves only one optical antenna, namely the host material, which limits the accessibility of excitation wavelength‐dependent (Ex‐De) PL. Consequently, the wider application of Ln3+ ions in light‐emitting devices is hindered. In this study, we present an organic–inorganic compound, (DMA)4LnCl7 (DMA+=[CH3NH2CH3]+, Ln3+=Ce3+, Tb3+), which serves as an independent host lattice material for efficient Ex‐De emission by doping it with trivalent antimony (Sb3+). The pristine (DMA)4LnCl7 compounds exhibit high luminescence, maintaining the characteristic sharp emission bands of Ln3+ and demonstrating a high PL quantum yield of 90–100 %. Upon Sb3+ doping, the compound exhibits noticeable Ex‐De emission with switchable colors. Through a detailed spectral study, we observe that the prominent energy transfer process observed in traditional host‐sensitized systems is absent in these materials. Instead, they exhibit two independent emission centers from Ln3+ and Sb3+, each displaying distinct features in luminous color and radiative lifetime. These findings open up new possibilities for designing Ex‐De emitters based on Ln3+ ions. [ABSTRACT FROM AUTHOR]

Directional defects management in polycrystalline perovskite film with inorganic passivator is highly demanded while yet realized for fabricating efficient and stable perovskite solar cells (PSCs). Here, we develop a directional passivation strategy employing a two‐dimensional (2D) material, Cu‐(4‐mercaptophenol) (Cu‐HBT), as a passivator precursor. Cu‐HBT combines the merits of the targeted modification from organic passivator and excellent stability offered by inorganic passivator. Featuring with dense organic functional motifs on its surfaces, Cu‐HBT has the capability to "find" and fasten to the Pb defect sites in perovskites through coordination interactions during a spin‐coating process. During subsequent annealing treatment, the organic functional motifs cleave from Cu‐HBT and convert in situ into p‐type semiconductors, Cu2S and PbS. The resultant Cu2S and PbS not only serve as stable inorganic passivators on the perovskite surface, significantly enhancing cell stability, but also facilitate efficient charge extraction and transport, resulting in an impressive efficiency of up to 23.5 %. This work contributes a new defect management strategy by directionally yielding the stable inorganic passivators for highly efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

Directional defects management in polycrystalline perovskite film with inorganic passivator is highly demanded while yet realized for fabricating efficient and stable perovskite solar cells (PSCs). Here, we develop a directional passivation strategy employing a two‐dimensional (2D) material, Cu‐(4‐mercaptophenol) (Cu‐HBT), as a passivator precursor. Cu‐HBT combines the merits of the targeted modification from organic passivator and excellent stability offered by inorganic passivator. Featuring with dense organic functional motifs on its surfaces, Cu‐HBT has the capability to "find" and fasten to the Pb defect sites in perovskites through coordination interactions during a spin‐coating process. During subsequent annealing treatment, the organic functional motifs cleave from Cu‐HBT and convert in situ into p‐type semiconductors, Cu2S and PbS. The resultant Cu2S and PbS not only serve as stable inorganic passivators on the perovskite surface, significantly enhancing cell stability, but also facilitate efficient charge extraction and transport, resulting in an impressive efficiency of up to 23.5 %. This work contributes a new defect management strategy by directionally yielding the stable inorganic passivators for highly efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

Sustainable water desalination and purification membrane processes require new practical pathways to improve their efficiency. To this end, the inclusion of two-dimensional materials in membrane structure has proven to have a significant impact in various applications. In particular, in processes such as membrane distillation and crystallization, these materials, thanks to their characteristics, help to increase the recovery of clean water and, at the same time, to improve the quality and the production of the recovered salts. Therefore, a fundamental aspect of obtaining 2D materials with certain characteristics is the technique used for the preparation. This review provides a broad discussion on the preparation and proprieties of 2D materials, including examples of organic structures (such as graphene and structures containing transition metals and organic metals). Finally, the critical challenges, future research directions, and the opportunities for developing advanced membranes based on 2D materials are outlined. [ABSTRACT FROM AUTHOR]

Molecular and charge arrangements in the solid state were controlled by a new building block: a triad molecule. Owing to the appropriate flexibilities in both molecular structure and electron distribution of the triad, the apparently simple salt exhibits an unstable metallic phase, which is promising for superconducting transitions. [ABSTRACT FROM AUTHOR]

Cervical cancer is the most prevalent reproductive malignancy that affects the female reproductive system. A myriad of anti-cancer compounds has been used for its treatment, but the increasing mortality rates are still devastating. Currently, organic metal complexes are gaining popularity due to their anti-cancer attributes. Therefore, the current work was designed to assess the therapeutic efficacy of non-functionalized multi-walled carbon nanotubes (N-MWCNT) and functionalized MWCNTs (F-MWCNT) against cervical cancer. Initially, N-MWCNTs and F-MWCNTs were structurally characterized by various parameters, including FTIR, XRD, TEM, SEM, AFM, and EDAX. Our comparative study revealed that F-MWCNTs have a larger surface area and the presence of OH and COOH as functional groups, which are uniformly distributed in the tubular and crystalline structure. Furthermore, the MTT assay revealed IC50 values of 47.70 µg/ml and 61.94 µg/ml of N- MWCNTs and F-MWCNT, respectively; in that relation, our immunoblot results show upregulation of BAX and downregulation of BCL-2 in either of the cases, with N-MWCNT having 2.92 and 0.45 folds in comparison to 2.68 and 0.41 folds of F-MWCNT. Our results revealed that both materials inhibited cell proliferation and induced apoptosis in a dose-dependent manner. Still, the effect of N-MWCNTs was more prominent as compared to F-MWCNTs. The overall conclusions of this study indicated that doses of F-MWCNTs could be explored for the safe drug delivery vehicle used as an effective biocompatible nanoformulation agent and this will open a new door for cervical cancer treatment. [ABSTRACT FROM AUTHOR]

Mechanically compliant conductors are of utmost importance for the emerging fields of soft electronics and robotics. However, the development of intrinsically deformable organic conductors remains a challenge due to the trade‐off between mechanical performance and charge mobility. In this study, we report a solution to this issue based on size‐selective ionic crosslinking. This rationally designed crosslinking mediated by length‐regulated oligo(ethylene glycol) pendant groups and metal ions simultaneously improved the softness and toughness and ensured excellent mixed ionic–electronic conductivity in poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate composite materials. Moreover, the added ions remarkably promoted accumulation of charge carriers in response to temperature gradient, thus offering a viable approach to stretchable thermoelectric generators with enhanced stability against humidity. [ABSTRACT FROM AUTHOR]

Mechanically compliant conductors are of utmost importance for the emerging fields of soft electronics and robotics. However, the development of intrinsically deformable organic conductors remains a challenge due to the trade‐off between mechanical performance and charge mobility. In this study, we report a solution to this issue based on size‐selective ionic crosslinking. This rationally designed crosslinking mediated by length‐regulated oligo(ethylene glycol) pendant groups and metal ions simultaneously improved the softness and toughness and ensured excellent mixed ionic–electronic conductivity in poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate composite materials. Moreover, the added ions remarkably promoted accumulation of charge carriers in response to temperature gradient, thus offering a viable approach to stretchable thermoelectric generators with enhanced stability against humidity. [ABSTRACT FROM AUTHOR]

Single‐atom catalysts (SACs) often show exceptionally high performance per metal loading. Besides benefiting from a better atom utilisation, the metal‐support interaction is more pronounced in SACs compared to traditional nanoparticle catalysts. Thus, using SACs in photochemical conversions is of great advantage where the rapid reactions often depend on the synergistic interaction of the active site with the photoactive support. Here we show the importance of this interaction by maximizing the active site/support interface using SACs. As an example, we examine the oxidation reaction of anthracene to anthracene‐9,10‐endoperoxide (EPO) in the presence of 0.1 wt% Pt/TiO2. Our SACs give a six‐fold improvement compared to dense packed nanoparticle catalysts (TOF=113 mMol Anthracene gPt−1 min‐−1 for the SAC). We attribute this to the synergy between the active site and the support. Moreover, we show that photocatalytic conversion is possible with photons of lower energy (2.7 eV) than the bandgap of pristine TiO2 (Eg=3.0–3.2 eV) thanks to organic doping of the metal oxide. [ABSTRACT FROM AUTHOR]

Friction stir welding is a technique of combining harmless for the environment because it doesn’t use flux or any other shield gas and doesn’t produce hazardous gas. To study the FSW process on composite material this work offers an experimental enquiry and optimisation technique. In this investigated how input process operating factors like tool rotational speed, feed rate and depth of cut affect an output parameter like hardness of welded connections and Ultimate Tensile Strength (UTS), Microstructure and metallurgical on the metal. To achieve this L27 Taguchi approach orthogonal array used to optimise design tests on friction stir welding parameters and also HCHCr tool used to improve the good weld ability and to increase the heat input. The experimental setup is run with several combinations of process parameters such as 900, 1000, and 1200 rpm of Tool rotational speed 20 mm, 25 and 30 mm as feed rate by adjusting the depth of cut values of 5.4 mm, 5.6 mm and 5.8 mm respectively. Additionally, utilising the regression analysis equations (ANOVA) used to identify the significant input parameters how it effects for the output metal structure. Finally, by achieved effective evaluation of the metallurgical and microstructure on the nylon 6A metal by various analysis and Testing. [ABSTRACT FROM AUTHOR]

Some times ago, in the framework of the Boltzmann kinetic equation in the so-called τ -approximation, it was shown that perpendicular resistivity in quasi-two-dimensional (Q2D) conductors can be impurity independent in a broad range of high parallel magnetic fields [A. G. Lebed and N. N. Bagmet, Phys. Rev. B 55 (1997) R8654]. In this paper, we demonstrate that this result is much more general than the Boltzmann kinetic equation in the τ -approximation and is valid in a pure Q2D metal at low frequencies of the electric field. The above-mentioned statement open possibilities to test the above discussed phenomenon in a number of Q2D organic, high-Tc, and some other Q2D superconductors in their metallic phases and gives a method to extract some important information about their Q2D Fermi surfaces. [ABSTRACT FROM AUTHOR]

Low‐dimensional (low‐D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low‐D OMHHs, especially the zero‐D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near‐unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6H5)4P]2SbCl5. In situ experimental characterizations and theoretical simulations reveal that the pressure‐induced electronic coupling between the lone‐pair electrons of Sb3+ and the π electrons of benzene ring (lp‐π interaction) serves as an unexpected "bridge" for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp‐π interactions in organic–inorganic hybrid systems. [ABSTRACT FROM AUTHOR]

Low‐dimensional (low‐D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low‐D OMHHs, especially the zero‐D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near‐unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6H5)4P]2SbCl5. In situ experimental characterizations and theoretical simulations reveal that the pressure‐induced electronic coupling between the lone‐pair electrons of Sb3+ and the π electrons of benzene ring (lp‐π interaction) serves as an unexpected "bridge" for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp‐π interactions in organic–inorganic hybrid systems. [ABSTRACT FROM AUTHOR]

Complexation of a copolymer of styrene and 5-methyl-5-hexene-2,4-dione with cobalt chloride in dimethylformamide occurs with the formation of metallopolymers of two types, namely with intra- and extramolecular binding of β-diketone groups, the ratio of which depends on the concentration of the initial macromolecular ligand. It has been established that the polymer metal complexes differ in the geometry of the coordination unit, molecular weights, and metal content resulting in the different reactivity to initiation of graft radical polymerization of methyl methacrylate. [ABSTRACT FROM AUTHOR]

Active waveguides have attracted growing attention as a basic component of miniaturized and integrated photonic devices. However, most optical waveguide materials suffer from severe self‐absorption, which greatly increases the optical loss. Therefore, developing highly efficient red‐emitting materials with large Stokes shift and negligible self‐absorption is of great interest. Herein, this work proposes a strategy to achieve both large Stokes shifts and high photoluminescence quantum yield (PLQY) in organic metal halide via large cation engineering. Two zero‐dimensional antimony(III) chlorides, (TMA)2SbCl5 and (TMAA)2SbCl5, are designed and synthesized by screening the ligands with different cationic volumes. Experimental and theoretical results reveal that the large cation can promote the self‐trapped excitons emission and improve stability. Benefiting from the large Stokes shift (291 nm) and high PLQY (98.3%), the as‐prepared (TMAA)2SbCl5 microplate exhibits efficient active waveguide with low loss coefficient of 6.07 × 10−3 dB µm−1. This work not only develops a novel active waveguide material, but also provides insights into the role of organic cation, which will provide new inspiration for the exploitation of excellent luminescent metal halides and photonic devices. [ABSTRACT FROM AUTHOR]

In organic transistors, the contact resistance at the interface between the organic semiconductor (OSC) and electrode reduces the device performance. To solve this problem, a buffer layer is inserted between the electrode and OSC layer to decrease the depletion layer that forms at the OSC surface. Especially in bottom-contact transistors, the effects of interfacial potentials and carrier traps can be suppressed using high-conductivity organic-conductors and carbon pastes as electrodes. Accordingly, a "self-contact" transistor was proposed based on chemically doping OSCs. This technique enables us to fabricate organic conductor electrodes specific to each OSC, resulting in transistors with low contact resistance. However, organic conductors based on OSCs are essential to expand the fabrication of these devices using the doping method. Consequently, OSCs have been used to develop a promising new class of organic conductors with high conductivity and excellent thermoelectric properties. Although developing organic conductors based on OSCs remains relatively unexplored, it is expected to become a new trend in functional molecular compounds. [ABSTRACT FROM AUTHOR]

The cobalt oxide (Co3O4) nanomaterials were prepared by coprecipitation synthesis technique by maintaining the pH of the mother solution at 7, 8, and 9. The prepared nanomaterials were subjected to structural and optical characterizations, and the results were examined. The optical absorption spectral studies reveal that the two absorption bands indicate ligand–metal coordination. The photoluminescence spectra contain emission peak at 488 and 745 nm due to size and shape of the synthesized materials. The magnetic nature of the samples was identified from the hysteresis loop traced by vibrating sample magnetometry (VSM). The Fourier transform infrared (FT-IR) spectrum of Co3O4 nanomaterials reveals two sharp bands absorbed in 584 and 666 cm-1. This ascribes to the Co-O and O-Co-O stretching, respectively. As the pH of the solution varied from 7 to 10, the SEM image authenticates the transformation of Co3O4 nanomaterials morphology from spherical to cubic to agglomerated shape. From the UV-Vis spectra, two absorption bands around 473 nm and 762 nm are observed for the materials prepared at pH 7 and 8. But at pH 9, these two peaks were shifted towards higher wavelengths 515 nm and 777 nm. The observed ferromagnetic nature of Co3O4 nanomaterials clearly show the role of surface spins and surface morphology on the magnetic properties of Co3O4 nanomaterials. The cyclic voltammetry (CV) curves show the rectangular type of voltammogram. This is an indication of good charge propagation with the electrodes. The Nyquist plots of Co3O4 nanomaterials have a semicircle in the high frequency region and a vertical line in the low frequency region. The results suggest that Co3O4 is found to be a promising material for the fabrication of light-emitting diodes, solar cells, and optoelectronic devices. [ABSTRACT FROM AUTHOR]

Coordination polymers have been a hot research topic in the field of biomedicine for their interesting bioactivities. To study the effects of metal ions on the bioactivity of the resulting coordination polymers, in this study, two novel coordination polymers, [Zn4(L)4(bix)4]·n(DMF)·4n(H2O) (1) and [Cd(L)(bix)(H2O)2]n·2n(H2O) (2) (H2L = 5-(1-oxoisoindolin-2-yl)isophthalic acid, bix = 5-(1-oxoisoindolin-2-yl)isophthalic acid, DMF = N,N′-dimethylformide), have been synthesized by the reactions of H2L, bix and Zn(II) or Cd(II) salts under the solvothermal condition and further characterized via the single crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and thermogravimetric analyses. The CIE chromaticity diagram indicated that complexes 1 and 2 are excellent blue luminescent materials. Their therapeutic effect with synergistic curcumin on post-stroke depression was explored in the present work. First of all, the analysis of enzyme-linked immunosorbent assay was exploited for testing the 5-hydroxytryptamine (5-HT) content exists in brain. Next, the serotonin transporter relative expression was also analyzed with the detection of real-time reverse transcription-polymerase chain reaction (RT-PCR). The experimental results show that the CP 1 could be a better candidate for synergistic curcumin for treating post-stroke depression by increasing 5-HT content and relative expression of serotonin transporter than CP 2. [ABSTRACT FROM AUTHOR]

Photoelectron spectra of early 3d-transition metal dioxide anions, Sc O 2 − , Ti O 2 − , V O 2 − , Cr O 2 − , and Mn O 2 − , are calculated using semilocal and hybrid density functional theory (DFT) and many-body perturbation theory within the GW approximation using one-shot perturbative and eigenvalue self-consistent formalisms. Different levels of theory are compared with each other and with available photoelectron spectra. We show that one-shot GW with a PBE0 starting point (G0W0@PBE0) consistently provides very good agreement for all experimentally measured binding energies (within 0.1 eV–0.2 eV or less). We attribute this to the success of PBE0 in mitigating self-interaction error and providing good quasiparticle wave functions, which renders a first-order perturbative GW correction effective. One-shot GW calculations with a Perdew–Burke–Ernzerhof (PBE) starting point do poorly in predicting electron removal energies by underbinding orbitals with typical errors near 1.5 eV. A higher exact exchange amount of 50% in the DFT starting point of one-shot GW does not provide very good agreement with experiment by overbinding orbitals with typical errors near 0.5 eV. While not as accurate as G0W0@PBE0, the G-only eigenvalue self-consistent GW scheme with W fixed to the PBE level provides a reasonably predictive level of theory (typical errors near 0.3 eV) to describe photoelectron spectra of these 3d-transition metal dioxide anions. Adding eigenvalue self-consistency also in W, on the other hand, worsens the agreement with experiment overall. Our findings on the performance of various GW methods are discussed in the context of our previous studies on other transition metal oxide molecular systems. [ABSTRACT FROM AUTHOR]

Self‐templating is a facile strategy for synthesizing porous carbons by direct pyrolysis of organic metal salts. However, the method typically suffers from low yields (<4%) and limited specific surface areas (SSA<2000 m2 g−1) originating from low activity of metal cations (e.g. K+ or Na+) in promoting construction and activation of carbon frameworks. Here we use cesium acetate as the only precursor of oxo‐carbons with large SSA of the order of 3000 m2 g−1, pore volume approaching 2 cm3 g−1, tunable oxygen contents, and yields of up to 15 %. We unravel the role of Cs+ as an efficient promoter of framework formation, templating and etching agent, while acetates act as carbon/oxygen sources of carbonaceous frameworks. The oxo‐carbons show record‐high CO2 uptake of 8.71 mmol g−1 and an ultimate specific capacitance of 313 F g−1 in the supercapacitor. This study helps to understand and rationally tailor the materials design by a still rare organic solid‐state chemistry. [ABSTRACT FROM AUTHOR]

Self‐templating is a facile strategy for synthesizing porous carbons by direct pyrolysis of organic metal salts. However, the method typically suffers from low yields (<4%) and limited specific surface areas (SSA<2000 m2 g−1) originating from low activity of metal cations (e.g. K+ or Na+) in promoting construction and activation of carbon frameworks. Here we use cesium acetate as the only precursor of oxo‐carbons with large SSA of the order of 3000 m2 g−1, pore volume approaching 2 cm3 g−1, tunable oxygen contents, and yields of up to 15 %. We unravel the role of Cs+ as an efficient promoter of framework formation, templating and etching agent, while acetates act as carbon/oxygen sources of carbonaceous frameworks. The oxo‐carbons show record‐high CO2 uptake of 8.71 mmol g−1 and an ultimate specific capacitance of 313 F g−1 in the supercapacitor. This study helps to understand and rationally tailor the materials design by a still rare organic solid‐state chemistry. [ABSTRACT FROM AUTHOR]

Monitoring the content of dissolved ozone in purified water is often mandatory to ensure the appropriate levels of disinfection and sanitization. However, quantification bears challenges as colorimetric assays require laborious off‐line analysis, while commercially available instruments for electrochemical process analysis are expensive and often lack the possibility for miniaturization and discretionary installation. In this study, potentiometric ionic polymer metal composite (IPMC) sensors for the determination of dissolved ozone in ultrapure water (UPW) systems are presented. Commercially available polymer electrolyte membranes are treated via an impregnation‐reduction method to obtain nanostructured platinum layers. By applying 25 different synthesis conditions, layer thicknesses of 2.2 to 12.6 µm are obtained. Supporting radiographic analyses indicate that the platinum concentration of the impregnation solution has the highest influence on the obtained metal loading. The sensor response behavior is explained by a Langmuir pseudo‐isotherm model and allows the quantification of dissolved ozone to trace levels of less than 10 µg L−1. Additional statistical evaluations show that the expected Pt loading and radiographic blackening levels can be predicted with high accuracy and significance (R2adj. > 0.90, p < 10−10) solely from given synthesis conditions. [ABSTRACT FROM AUTHOR]

N‐Type thermoelectrics typically consist of small molecule dopant+polymer host. Only a few polymer dopant+polymer host systems have been reported, and these have lower thermoelectric parameters. N‐type polymers with high crystallinity and order are generally used for high‐conductivity (σ ${\sigma }$) organic conductors. Few n‐type polymers with only short‐range lamellar stacking for high‐conductivity materials have been reported. Here, we describe an n‐type short‐range lamellar‐stacked all‐polymer thermoelectric system with highest σ ${\sigma }$ of 78 S−1, power factor (PF) of 163 μW m−1 K−2, and maximum Figure of merit (ZT) of 0.53 at room temperature with a dopant/host ratio of 75 wt%. The minor effect of polymer dopant on the molecular arrangement of conjugated polymer PDPIN at high ratios, high doping capability, high Seebeck coefficient (S) absolute values relative to σ ${\sigma }$ , and atypical decreased thermal conductivity (κ ${\kappa }$) with increased doping ratio contribute to the promising performance. [ABSTRACT FROM AUTHOR]

N‐Type thermoelectrics typically consist of small molecule dopant+polymer host. Only a few polymer dopant+polymer host systems have been reported, and these have lower thermoelectric parameters. N‐type polymers with high crystallinity and order are generally used for high‐conductivity (σ ${\sigma }$) organic conductors. Few n‐type polymers with only short‐range lamellar stacking for high‐conductivity materials have been reported. Here, we describe an n‐type short‐range lamellar‐stacked all‐polymer thermoelectric system with highest σ ${\sigma }$ of 78 S−1, power factor (PF) of 163 μW m−1 K−2, and maximum Figure of merit (ZT) of 0.53 at room temperature with a dopant/host ratio of 75 wt%. The minor effect of polymer dopant on the molecular arrangement of conjugated polymer PDPIN at high ratios, high doping capability, high Seebeck coefficient (S) absolute values relative to σ ${\sigma }$ , and atypical decreased thermal conductivity (κ ${\kappa }$) with increased doping ratio contribute to the promising performance. [ABSTRACT FROM AUTHOR]

All‐perovskite tandem solar cells are promising for breaking through the single‐junction Shockley–Queisser limit, and that potentially raises interest in configuring efficient Sn‐Pb alloyed narrow‐bandgap perovskite solar cells (PSCs). However, the Sn‐Pb alloyed perovskites are commonly plagued by uncontrollable crystallization dynamics and severe p‐doping levels. Herein, an effective additive molecule is designed with heterovalent substitution and antioxidant functions, whereby an organic metal coordination compound of tris(2,4‐pentanedionato)gallium (TPGa) is employed to upgrade the quality of perovskite films. Ga3+ substitution obviously boosts the formation energy of Sn vacancies and heals the trap states. Meanwhile, the crystal structure evolution process is improved by the anchoring effect of 2,4‐pentanedionato. The PSCs incorporating these improvements deliver not only a power conversion efficiency of 21.5% but also outstanding stability, as demonstrated by retaining 80% of the initial efficiency for over 1500 h. In addition, 23.14%‐efficient all‐perovskite tandem solar cells are further obtained by pairing this PSC with a wide‐bandgap (1.74 eV) top cell. This study supports the feasibility of doping trivalent ions into the Sn‐Pb alloyed perovskites to compromise the self‐p‐doping effect and highlights the importance of acetylacetone for passivating defects and hindering oxidation. [ABSTRACT FROM AUTHOR]

Polymer single crystals are used as templates to synthesize polymer brushes, known as the "polymer‐single‐crystal‐assisted‐grafting‐to" (PSCAGT) approach. Polymer brushes with controlled grafting densities and spatial tethering locations are demonstrated. Previous works focused on solution crystallization, which involves large amounts of organic solvent, and the grafting density can only be tuned by varying crystallization temperatures. In this work, thin film crystallization is utilized to fabricate 2D polymer crystals on flat surfaces. Subsequent chemical tethering leads to polymer brushes that retain the original morphology of the crystals with high fidelity. Furthermore, it is shown that the grafting density of the polymer brushes fabricated using this method depends on the chain end distribution on the top/bottom surfaces of the crystal, which can be facilely controlled by annealing the crystals at various nonsolvent media. This work broadens the scope of the PSCAGT method and provides a new route to achieve polymer brushes with controlled structures. [ABSTRACT FROM AUTHOR]

The condensation reaction between 5‐amino‐1,3,4‐thiadiazole‐2‐thiol and 1,2‐dibromoethane to afford the ligand L was carried out in direct to obtain the desired organic ligand. New [Er(L)ClH2O]Cl2·3H2O, [Yb(L)(H2O)2]Cl3·4H2O, and [Ta(L)Cl2]Cl3·4H2O complexes have been prepared from (L) by reacting one mole from metal ions with one mole from L. In addition to their physical characteristics, they were described using spectroscopic techniques (infrared [IR], nuclear magnetic resonance [NMR], and UV–Vis), gas chromatography (GC)‐mass, and X‐ray powder diffraction. Further interpretation of complex structures was supported by measurements of molar conductivity, magnetic susceptibility, mole ratio, and thermodynamic investigations in addition to theoretical study through the use of density functional theory and characterization techniques. IR spectral data showed the mode of action of the neutral tetradentate L ligand and its coordination via two N‐amine and two S‐thiols. The octahedral geometry surrounding the central lanthanide ions was suggested by the magnetic moments, diffused reflectance, and spectral data. Molar conductivity results exposed that Yb(III) and Ta(V) chelates were 1:3 electrolytes and Er(III) chelate was 1:2 electrolyte. In addition, practically all the complexes demonstrated effective antimicrobial activity against Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, and Staphylococcus aureus species, via inhibition zone diameters in 9–15 mm mg−1 range. However, neither Candida albicans nor Aspergillus flavus species were susceptible to their antifungal effects. Finally, molecular docking (MOE) experiments showed the significant binding affinity of the ligand and its complexes with several 6KOC, 6LU4, and 6LU4 protein receptors. Finally, it is important to emphasize that these complexes may be potential antioxidant agents according to the biochemical results. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PP) methods were accustomed to examine the corrosion inhibition of aluminum silicon alloys (AlSi) in 1 M HCl solution. Experimental measurements indicate that the thiadiazole ligand reduces the corrosion rate. [ABSTRACT FROM AUTHOR]

As high-order harmonic emitters, quantum dots are produced through laser-induced plasmas. Subsequently, we generate high-order harmonics with 800-nm and 30-fs pulses from laser-produced plasmas containing quantum dots of different metal sulfides (Ag2S, CdS, and Cd0.5Zn0.5S). The high-order harmonic generation is analyzed using different approaches, including two-color (800 nm + 400 nm) pump, application of alloyed quantum dots, and quasiphase matching of interacting waves. We discuss the self-phase modulation induced splitting of harmonics, the difference in the application of thick and thin crystals for second harmonic (400 nm) emission during two-color pumping of the quantum dot plasma, the spatial modulation of the quantum dot plasma for quasiphase matching, and the comparison of harmonic yields from monomer and quantum dot plasmas. This study allows us to determine the mechanisms of coherent extreme ultraviolet radiation generation using a few nanometer-sized emitters as well as optimal methods for further enhancing the high-order harmonic generation efficiency. [ABSTRACT FROM AUTHOR]

We present a coarse-grained model for using dissipative particle dynamics simulations to study the interaction between cis-1,4 polybutadiene polymer chains and a metal oxide (Cu2O) surface at the mesoscopic scale. We employ a bottom-up approach in order to link the structural properties with their underlying molecular properties over a wide range of time and length scales. The parameterization of the model was realized using a recently developed Bayesian scheme that is based on trajectory matching of an atomistic description of the system. The model is used to investigate the local structure of polymers in a confined slab geometry by means of density profiles, radius of gyration, orientation with respect to the surface, and their adsorption. [ABSTRACT FROM AUTHOR]

Experimental research has shown that much less charge injection occurs in polytetrafluoroethylene (PTFE) compared to polyethylene (PE). To clarify the mechanisms of charge injection from metals into polymer insulators, we comparatively studied charge injection in PE and PTFE oligomers using first-principles calculations. Two different models were studied: chemisorption (bonding) and physisorption (nonbonding). The results show that the electron injection barrier of the metal/PTFE interface is larger than that of the metal/PE interface only in the case of chemisorption. The larger electron injection barrier of the metal/PTFE oligomer interface is mainly affected by the positive vacuum level shift of the metal/PTFE interface induced by electron transfer from the metal to PTFE along the chemical bonds. In the case of physisorption, the hole injection barrier of the metal/PTFE interface is larger than that of the metal/PE interface. This is attributed to the larger ionization potential of PTFE compared to PE. The calculated results reasonably explain the experimental phenomena. The agreement between the experimental and calculated results verifies the rationality of our calculation models. The models used herein can likely be applied in other metal/polymer interfacial systems with acceptable accuracy. [ABSTRACT FROM AUTHOR]