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New Y-shaped ferrocene (Fc)-conjugated trifluoromethyl-substituted imidazole (IM) donor–π–acceptor [(D–π)2–IM–D′–π–CF3] "push–pull" chromophores [(Fc–CH＝CH)2–IM–C6H4–R–C6H4–CF3] {R= –OCH3 (1); –N(C2H5)2 (2)} were synthesized and structurally characterized. The structure of the chromophores was confirmed via single-crystal X-ray diffraction studies. They crystallized in the triclinic P1¯ (for 1) and monoclinic P21/c (for 2) space groups. Thermogravimetric analysis (TGA) was used to study the thermal stability of chromophores 1 and 2, and it was found that both were stable at temperatures of about 300 °C. The redox properties were studied through cyclic voltammetry (CV), which revealed one-electron transfer from the ferrocene to ferrocenium ion (Fe2+ Fe3+), and their potentials were utilized to calculate their energy gaps, which were 2.16 eV for 1 and 2.12 eV for 2. The second-order nonlinear optical (NLO) properties of chromophores 1 and 2 were explored via electric-field-induced second-harmonic generation (EFISH) technique in CHCl3 solution with an incident wavelength of 1907 nm. μβEFISH values were −725 × 10−48 esu and −806 × 10−48 esu for 1 and 2, respectively. The μβEFISH values slightly decreased compared with other reported ferrocene-conjugated Y-shaped imidazole chromophores owing to their substitution on imidazole nitrogen, which increases steric hindrance and reduces the ICT process in the chromophores. In addition, their frontier molecular orbital levels, excited and ground state dipole moments (μe and μg), and electronic absorption spectra were studied using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) with the B3LYP method using the 6-31+G** basis set. [ABSTRACT FROM AUTHOR]

Ylide‐functionalized phosphines (YPhos) have been shown to yield highly active gold catalysts owing to their high donor capacity. To examine the impact of ylide functionalization on a given ligand structure, a series of ferrocenyl diphosphines functionalized with no, one or two ylide moieties and their corresponding bimetallic gold complexes were prepared. The complexes feature an anti‐conformation of the two phosphine moieties, guaranteeing the presence of two independent metal centers. Comparative studies of the complexes in the hydroamination and hydrohydrazination of alkynes revealed a significant increase in catalytic activity for each newly introduced ylide group. The di‐YPhos ligands were revealed to be the most active precatalysts, functioning effectively even at 0.1 or 0.2 mol % catalyst loading. This catalytic efficiency was demonstrated for a series of alkynes, amines and hydrazines. [ABSTRACT FROM AUTHOR]

In this work, a computational investigation of ferrocene (Fc)‐based compounds FcCH2CS3CH2Fc (1) and FcCH2SSCH2Fc (2) sensitizer for dye‐sensitized solar cells (DSSCs) has been carried out to comprehend the photophysical and photo‐electrochemical properties. The density functional theory (DFT) and time‐dependent DFT (TD‐DFT) were employed to assess the photovoltaic parameters of the compounds. The frontier molecular orbital analysis revealed the electron density distribution at HOMO and LUMO, which clearly demonstrates the charge separation within the compounds. The electronic absorption spectra are simulated using the TD‐DFT method to comprehend the ability of the compounds to harvest sunlight and efficiently act as photosensitizer. Simulation of electronic spectra of dye@TiO2 cluster exhibits that the absorption coefficient of compound 1 is higher than compound 2 due to the greater extent of charge transfer from the dye to the TiO2 cluster. These computational findings are corroborated by the reported photovoltaic performance of the compounds. [ABSTRACT FROM AUTHOR]

An approach for the preparation and stabilization of primary phosphine oxides is presented complementing previous methods of in situ generation. Specifically, RP(O)H2 where R=benzyl (Bn), cyclohexyl (Cy), 2‐naphthyl (2‐Naph), phenyl (Ph), tert‐butyl (t‐Bu) was prepared by controlled oxidation of the corresponding primary phosphine in presence of ferrocene as stabilizing reagent. The primary phosphine oxides were characterized using NMR and MS and studied in twofold hydrophosphorylation of diketones. The domino‐phospha‐aldol reaction catalysed with 5 mol% of sodium methoxide yielded five‐, six‐ and seven‐membered heterocyclic tertiary phosphine oxides with a high degree of stereoselectivity, as confirmed by single X‐ray diffraction. [ABSTRACT FROM AUTHOR]

The document is the contents list for an issue of the journal Chemical Communications. It includes the titles and authors of various articles and features that will be included in the issue. Some of the topics covered include silk-based intelligent fibers and textiles, advances in molecular engineering of perovskite heterostructures, and metal-organic framework based self-powered devices for human body energy harvesting. The journal is published by The Royal Society of Chemistry, a leading chemistry community. [Extracted from the article]

A ferrocene-modified COF, namely Ni-Tph-COF-Fc, was synthesized and applied in OER. Compared with Ni-Tph-COF-OH, Ni-Tph-COF-Fc shows improved performance with a current density of 99.6 mA cm−2, an overpotential of 450 mV, and a Tafel slope of 73.1 mV dec−1, which may be attributed to a synergy between introduced ferrocene and metalloporphyrin in the COFs. Moreover, the enhanced OER performance leads to an improved CO2RR performance with an FECO of 93.1%. This work represents an effective strategy to enhance the anodic OER performance and realize efficient CO2RR. [ABSTRACT FROM AUTHOR]

Pyridine-alkoxide (pyalk) ligands that support transition metals have been studied for their use in electrocatalytic applications. Herein, we used the pyalk proligands diphenyl(pyridin-2-yl)methanol ([H]PhPyalk, L1), 1-(pyren-1-yl)-1-(pyridin-2-yl)ethan-1-ol ([H]PyrPyalk, L2), 1-(pyridine-2-yl)-1-(thiophen-2-yl)ethan-1-ol ([H]ThioPyalk, L3), and 1-(ferrocenyl)-1-(pyridin-2-yl)ethan-1-ol ([H]FePyalk, L4) to synthesize CuII complexes that vary in nuclearity and secondary coordination sphere. Also, the proligand 1-(ferrocenyl)-1-(5-methoxy-pyridin-2-yl)ethan-1-ol ([H]FeOMePyalk, L5) was synthesized with a methoxy substituted pyridine; however, the isolation of a CuII complex ligated by L5 was not possible. Under variable reaction conditions, the pyalk ligands reacted with CuII precursors and formed either mononuclear or dinuclear CuII complexes depending on the amount of ligand added. The resulting complexes were characterized by single crystal X-ray diffraction, elemental analysis, and cyclic voltammetry. [ABSTRACT FROM AUTHOR]

In the pursuit of fabricating functional ceramic nanostructures, the design of preceramic functional polymers has garnered significant interest. With their easily adaptable chemical composition, molecular structure, and processing versatility, these polymers hold immense potential in this field. Our study succeeded in focusing on synthesizing ferrocene-containing block copolymers (BCPs) based on polyacrylonitrile (PAN). The synthesis is accomplished via different poly(acrylonitrile-block-methacrylate)s via atom transfer radical polymerization (ATRP) and activators regenerated by electron transfer ATRP (ARGET ATRP) for the PAN macroinitiators. The molecular weights of the BCPs range from 44 to 82 kDa with dispersities between 1.19 and 1.5 as determined by SEC measurements. The volume fraction of the PMMA block ranges from 0.16 to 0.75 as determined by NMR. The post-modification of the BCPs using 3-ferrocenyl propylamine has led to the creation of redox-responsive preceramic polymers. The thermal stabilization of the polymer film has resulted in stabilized morphologies based on the oxidative PAN chemistry. The final pyrolysis of the sacrificial block segment and conversion of the metallopolymer has led to the formation of a porous carbon network with an iron oxide functionalized surface, investigated by scanning electron microscopy (SEM), energy dispersive X-ray mapping (EDX), and powder X-ray diffraction (PXRD). These findings could have significant implications in various applications, demonstrating the practical value of our research in convenient ceramic material design. [ABSTRACT FROM AUTHOR]

The metallocenes ferrocene (Cp2Fe, 1), nickelocene (Cp2Ni, 2), and cobaltocene (Cp2Co, 3) crystallize in the same space group (P21/a) and they have the same shape and similar size. Therefore, they form solid solutions with random distribution of the different molecules when crystallized from solution. Alternatively, the solid metallocenes can be ground together manually, and the solid solutions form at any molar ratio within minutes. The metallocenes 2 and 3 are paramagnetic. Solid solutions of 1/3 and 2/3 have been studied by paramagnetic solution and solid-state NMR spectroscopy. The effect of the paramagnetic species on the other components in the solid solutions has been investigated. The impact on the chemical shifts is limited. However, the halfwidths and the signal shapes, as defined by the rotational sideband intensities, change with increasing amounts of paramagnetic components. The 1H T1 relaxation times are shortened for diamagnetic protons in the presence of paramagnetic metallocenes in the solid solutions. It has been demonstrated that all metallocenes mix at the molecular level within the polycrystalline samples. The EPR spectra of the solid solutions are dominated by the most intensive signal of any paramagnetic metallocene in the solid samples. [ABSTRACT FROM AUTHOR]

Hematite (α-Fe2O3) is one of the most promising and widely used semiconductors for application in photoelectrochemical (PEC) water splitting, owing to its moderate bandgap in the visible spectrum and earth abundance. However, α-Fe2O3 is limited by short hole-diffusion lengths. Ultrathin α-Fe2O3 films are often used to limit the distance required for hole transport, therefore mitigating the impact of this property. The development of highly controllable and scalable ultrathin film deposition techniques is therefore crucial to the application of α-Fe2O3. Here, a plasma-enhanced atomic layer deposition (PEALD) process for the deposition of homogenous, conformal, and thickness-controlled α-Fe2O3 thin films (<100 nm) is developed. A readily available iron precursor, dimethyl(aminomethyl)ferrocene, was used in tandem with an O2 plasma co-reactant at relatively low reactor temperatures, ranging from 200 to 300 °C. Optimisation of deposition protocols was performed using the thin film growth per cycle and the duration of each cycle as optimisation metrics. Linear growth rates (constant growth per cycle) were measured for the optimised protocol, even at high cycle counts (up to 1200), confirming that all deposition is 'true' atomic layer deposition (ALD). Photoelectrochemical water splitting performance was measured under solar simulated irradiation for pristine α-Fe2O3 deposited onto FTO, and with a α-Fe2O3-coated TiO2 nanorod photoanode. [ABSTRACT FROM AUTHOR]

A bis-ferrocene macrocycle was synthesized by reversible acylhydrazone formation under thermodynamic control, starting from a ferrocene functionalized with hydrazide and protected aldehyde moieties. A hydrogen sulfate anion acts as a template to direct the synthesis specifically toward the macrocyclic dimer, due to a weak but selective binding interaction. This work highlights the utility of dynamic combinatorial chemistry as an approach to macrocycle synthesis. [ABSTRACT FROM AUTHOR]

The present study proposes an innovative transdermal drug delivery system using ferrocene-incorporated fibers to enhance the bioavailability and therapeutic efficacy of ascorbyl tetraisopalmitate. Using electrospinning technology, the authors created ferrocene polymer fibers capable of highly efficient drug encapsulation and controlled release in response to reactive oxygen species commonly found in wound sites. The approach improves upon previous methods significantly by offering higher drug loading capacities and sustained release, directly targeting diseased cells. The results confirm the potential of ferrocene fibers for localized drug delivery, potentially reducing side effects and increasing patient convenience. The method could facilitate the application of bioactive compounds in medical textiles and targeted therapy. [ABSTRACT FROM AUTHOR]

Ferrocene‐based derivatives play significant roles in biomedicine and catalytic reactions. This article demonstrates the C–O/N/S formation reactions of α‐ferrocenyl alcohols under mild conditions using the organic compound NTBC (2,2′,2″‐(nitrilotris (methylene))tris(1H‐benzo[d]imidazole‐5‐carboxylic acid)) as the catalyst. The catalyst is utilized in amounts of 5 mol% or less, and the majority of substrates yield derivatized products in good to excellent yields. This metal‐free catalytic method shows promising applications in the synthesis of pharmaceutical intermediates for its no metal pollution. [ABSTRACT FROM AUTHOR]

The chemical synthesis of 5-(4-azidophenyl)-10,15,20-tris(2-furyl/2-thienyl)porphyrins and their utilization in a Cu(I) catalyzed alkyne-azide 'click' reaction (CuAAC) with ethynylferrocene to obtain the hitherto unknown meso-tris(2-furyl/2-thienyl) substituted porphyrin–ferrocene 'click' conjugates are reported. These new 'click' conjugates were studied along with the reference 'click' conjugates containing all-meso-aryl substituted porphyrins by experimental and computational methods. Compared to the reference, the new conjugates displayed red-shifted absorption/emission bands, easier porphyrin ring reduction, and an efficient photoinduced electron transfer (PET) process from ferrocene to a porphyrin unit. Density functional theory (DFT) calculations performed on these conjugates revealed a good correlation with the experimental results. [ABSTRACT FROM AUTHOR]

The incorporation of different ferrocene scaffolds into the peptide sequences induces the formation of hydrogen-bond-based secondary structural elements that are frequently observed in natural peptides and proteins. There are three simple ferrocene scaffolds for conjugation with amino acids and peptides that serve as templates for ferrocene peptidomimetics, namely ferrocene-1,1′-dicarboxylic acid (Fcd, I), 1′-aminoferrocene-1-carboxylic acid (Fca, III), and ferrocene-1,1′-diamine (Fcda, V). Here, we have investigated their ability to induce the turn structure upon conjugation with Val, Leu, and Phe. Furthermore, we also wanted to determine whether the branched side chains of Val, Leu, and Phe interfere with intramolecular hydrogen bonding (IHB). For these purposes, we performed a detailed spectroscopic analysis by measuring the concentration, temperature, and solvent dependence of the IR, NMR, and CD spectra. The effect of the different ferrocene scaffolds on the antioxidant activity of the prepared peptides was tested using the DPPH and ABTS methods, and was further rationalized using electrochemical measurements. It was found that the ferrocene scaffold has the greatest influence on the hydrogen bonding pattern, while the influence of the side branches of the amino acids is less relevant. [ABSTRACT FROM AUTHOR]

The medicinal chemistry of ferrocene has gained its momentum after the discovery of biological activities of ferrocifen and ferroquine. These ferrocenyl drugs have been designed by replacing the aromatic moiety of the organic drugs, tamoxifen and chloroquine respectively, with a ferrocenyl unit. The promising biological activities of these ferrocenyl drugs have paved a path to explore the medicinal applications of several ferrocenyl conjugates. In these conjugates, the ferrocenyl moiety has played a vital role in enhancing or imparting the anticancer activity to the molecule. The ferrocenyl conjugates induce the cytotoxicity by generating reactive oxygen species and thereby damaging the DNA. In medicinal chemistry, the five membered nitrogen heterocycles (azoles) play a significant role due to their rigid ring structure and hydrogen bonding ability with the biomolecules. Several potent drug candidates with azole groups have been in use as chemotherapeutics. Considering the importance of ferrocenyl moiety and azole groups, several ferrocenyl azole conjugates have been synthesized and screened for their biological activities. Hence, in the view of a wide scope in the development of potent drugs based on ferrocenyl azole conjugates, herein we present the details of synthesis and the anticancer activities of ferrocenyl compounds bearing azole groups such as imidazole, triazoles, thiazole and isoxazoles. [ABSTRACT FROM AUTHOR]

Abstract The present study proposes an innovative transdermal drug delivery system using ferrocene-incorporated fibers to enhance the bioavailability and therapeutic efficacy of ascorbyl tetraisopalmitate. Using electrospinning technology, the authors created ferrocene polymer fibers capable of highly efficient drug encapsulation and controlled release in response to reactive oxygen species commonly found in wound sites. The approach improves upon previous methods significantly by offering higher drug loading capacities and sustained release, directly targeting diseased cells. The results confirm the potential of ferrocene fibers for localized drug delivery, potentially reducing side effects and increasing patient convenience. The method could facilitate the application of bioactive compounds in medical textiles and targeted therapy.

[Display omitted] • Embedding of electron-rich cloud groups enhances material conductivity and enhances material stability. • Embedded ferrocene weakens the force of hydrogen bonding formed during ammonium-ion storage in the VOH interlayer. • This work provides an attempt of PTCDI//Fer/VOH full cell to apply AAIBs for practical applications and full battery packs. Aqueous ammonium ion batteries (AAIBs) are garnering increasing attention due to their utilization of abundant resources, cost-effectiveness, safety, and unique energy storage mechanism. The pursuit of high-performance cathode materials has become a pressing issue. In this study, we propose and synthesize ferrocene-embedded hydrated vanadium pentoxide (Fer/VOH) for implementation in AAIBs. The inclusion of ferrocene serves to expand the interlayer spacing, mitigate interlayer forces, and introduce the electron-rich environment characteristic of ferrocene. This augmentation facilitates the creation of additional oxygen vacancies, substantially enhancing the capacity and efficiency of ammonium ion storage. Notably, our investigation reveals that the incorporation of ferrocene attenuates the hydrogen bonding interactions associated with ammonium ions, rendering them more amenable to the interlayer embedding and release processes. Building upon these advantages, Fer/VOH exhibits a specific capacity of 313 mAh/g at a current density of 0.2 A/g, representing the highest reported performance among vanadium oxides utilized in AAIBs to date. Even after 2000 charge/discharge cycles at a current density of 2 A/g, Fer/VOH maintains a reversible specific capacity of 89 mAh/g, with a capacity retention rate of 54.8%. This study confirms the viability of Fer/VOH as a cathode material for AAIBs and offers a novel approach to enhancing the electrical conductivity and diminishing the hydrogen bonding forces in vanadium oxide intercalation through the embedding of electron-rich species and positronic groups. [ABSTRACT FROM AUTHOR]

Abstract A series of 4-ferrcenylbutyl carboxylate esters with different alkyl chain length (C2-C4) of carboxylic acids were synthesized using Fe3O4@SiO2@(CH2)3-Im-bisEthylFc[I] nanoparticles as catalyst and have been characterized with FT-IR, 1H NMR, and 13C NMR. Ferrocenyl-based esters were used as corrosion inhibitors of mild steel in the 1M HCl solution as corrosive media. The corrosion inhibition efficiency of the synthesized ferrocenyl-based esters has been assessed by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The 4-ferrocenylbutyl propionate showed a more effective corrosion inhibition behavior among the studied esters with 96% efficiency after immersion in the corrosive media for 2 weeks. The corrosion inhibition mechanism is dominated by formation of passive layer of inhibitor on the surface of the mild steel by adsorption. Moreover, the adsorption characteristics of 4-butylferrcenyl carboxylate esters on mild steel were thoroughly explored using density functional theory calculations. It was found that the Fe atoms located around the C impurity in the mild steel are the most efficient and active sites to adsorb 4-butylferrcenyl carboxylate esters.

Ferrocene (FeCp2) was introduced as a non-magnetic guest molecule to activated carbon fibers (ACFs) as a nanographene-based host having localized spins originating from zigzag edges of graphene. The introduction of the guest molecule was confirmed by FTIR for ACFs-FeCp2 introduced at 55 (150) °C (FeCp2-ACFs-55(150)). The appearance of satellite Fe2p peaks and the increase in shake-up peak intensity of the C1s in the XPS spectrum proved the emergence of charge-transfer host–guest interaction in FeCp2-ACFs-150, supported by the red-shift of the G-band in the Raman spectrum. The six-times enhancement in the spin concentration in FeCp2-ACFs-150 compared with ACFs indicates the spin magnetism of the non-magnetic guest FeCp2+ molecule induced by a charge-transfer host–guest interaction in the nanographene host. The larger ESR linewidth than that expected from the dipolar interaction estimated by the localized spin concentration suggests the exchange interaction between the nanographene and FeCp2 spins. The narrowing of the ESR linewidth of FeCp2-ACFs-55 upon higher excitation microwave power suggests the inhomogeneity of the environment for FeCp2+ molecules in the nanographene host. The observed induction of spin magnetism by the interfacial interactions between the nanographene host and the guest molecules will be a promising strategy for developing a new class of molecular magnets.

The production of Li2CO3/C through CO2 reduction reaction in nonaqueous systems is a complex four‐electron, multi‐step process, and the short existence time of intermediate monomers is not conducive to observation, which causes great difficulties in clarifying and regulating the CO2 reduction path. Herein, ferrocene (Fc) as a functional additive into the electrolyte can stabilize the discharge intermediates and favor the occurrence of the two‐electron reaction path during CO2RR, which leads to more stable operation of the Li‐CO2 battery; with the assistance of Fc, the CO2 reduction pathway in Li‐CO2 battery is also clarified. Theoretical calculation analysis combined with experimental characterization observation confirms that Fc can shorten the CO2 reduction distance through interaction with CO2 and affecting the solvent environment around Li+, stabilize intermediate products to clarify the discharge path. The existence time of intermediates and discharge depth of the battery are key factors affecting the CO2 reduction pathway. The Li2C2O4 formed by CO2 reduction through the 2‐electron pathway is more favorable for the reversible operation of the Li‐CO2 battery than Li2CO3/C through the 4‐electron pathway. This work provides inspiration for clarifying the reaction mechanism and regulating the CO2 reduction pathway to improve the electrochemical performance of Li‐CO2 battery in the future. [ABSTRACT FROM AUTHOR]

The Raman spectra of ferrocene crystals were measured at pressures up to 20 GPa, and an abnormally large bandwidth of intermolecular phonons at ambient pressure was found. With an increase in the pressure, the bandwidth increased to a maximum at ~2 GPa and then decreased to a minimum at ~4 GPa, which was equal to the pressure‐independent bandwidth of intramolecular phonons. The unusual behavior of the bandwidth was related to the instability of a ferrocene molecule caused by jumps between its D5d and D5h conformations. A decrease in the time of jumps between the conformations to the period of crystal lattice vibrations led to a loss of coherence and broadening of intermolecular phonon bands. The energy barrier between the conformations was determined to be ~17.6 meV/molecule under ambient conditions and 80 meV/molecule at 4.9 GPa. An increase in the barrier with pressure was due to the enhancement of the crystal field, which resulted in the inhibition of the jumps and the stabilization of the molecule in the D5d conformation. [ABSTRACT FROM AUTHOR]

Metal complexes have a significant impact on the treatment of human cancer. However, the scarcity of these compounds, resulting from their limited synthesis, hinders the comprehensive investigation of their anticancer mechanisms. Organic palladium compounds, known for their distinctive stability and properties, are thus an essential area of research in the development of anti‐tumor therapy. In our study, we synthesized two novel ferrocene cyclopalladated compounds (C2 and C4). Its configuration was thoroughly characterized by employing 1H, 13C NMR, ESI‐MS, and elemental analysis techniques. The molecular structures were determined by X‐ray single‐crystal diffraction. In an in vitro anticancer study, it was observed that both C2 and C4 exhibited excellent suppression of viability in various tumor cell lines. These compounds showed better potency than cisplatin and demonstrated lower toxicity in normal cells. Particularly, C4 displayed approximately 22 times greater potency than cisplatin in suppressing melanoma cells (B16F10). Our study suggests that ferrocene cyclopalladated compounds have the potential to be promising candidates for the development of innovative anticancer drugs. [ABSTRACT FROM AUTHOR]

A series of substituted ferrocenyl boron derivatives was synthesized. The oxidation of the ferrocenyl unit resulted in a significant increase of the boron‐centered Lewis acidity. The neutral and cationic Lewis acids were characterized by NMR spectroscopy, crystal structure analysis and by computational methods. The new Lewis acids were then applied in the Meinwald rearrangement of epoxides, predominantly furnishing aldehydes as the kinetic products. [ABSTRACT FROM AUTHOR]

We present herein the synthesis, characterization and complexation of ferrocenyl‐substituted MIIs (mesoionic imines) and their metal complexes. In the free MIIs, strong hydrogen bonding interactions are observed between the imine‐N and the C−H bonds of the ferrocenyl substituents both in the solid state and in solution. The influence of this hydrogen bonding is so strong that complexation of the MIIs with [IrCp*Cl2]2 yields unique six‐membered iridacycles via C−H‐activation of the corresponding C−H‐site at the Fc‐substituent and not the Ph‐substituent. This result is in contrast to previous reports in which always a preferential C−H activation at the phenyl substituent is observed in competitive reactions in the presence of ferrocenyl substituents. The corresponding Ir complexes formed after in‐situ halide exchange reaction exist in either [Ir−I] contact or as [Ir]+I− solvent separated ion‐pairs depending on the solvent polarity. The iodide coordinated and solvent separated ion‐pairs display drastically different physical properties. The TEP (Tolman‐electronic‐parameter) of these ligands was determined and lines up with previously reported MII‐ligands. The redox properties were investigated by a combination of electrochemical and spectroelectrochemical methods. We show here how non‐covalent interactions can have a drastic influence on the physical and chemical properties of these new class of compounds. [ABSTRACT FROM AUTHOR]

New and effective D–π–A and D–π–A–π–A systems of chromophores 1–4 based on the ferrocene core have been synthesized using Knoevenagel condensation reactions and the characterization of chromophores 1–4 was done by modern spectroscopic methods. Moreover, 2 and 4 structures were confirmed using the single crystal X-ray diffraction (SC-XRD) technique. Crystal packing revealed that the chromophores are centrosymmetric and show non-covalent interactions. The observed positive solvatochromism reveals that the stabilization of molecules is greater in excited states than in the ground states. The fluorescence spectra of all the chromophores display weak emission in the solution state, and enhanced emission was observed in a THF:H2O mixture, due to the restriction of intramolecular rotation (RIR), and it is known as aggregation-induced emission (AIE). The SHG (second harmonic generation) measurements were done by the Kurtz–Perry powder method with potassium dihydrogen phosphate (KDP) as a reference material. The presence of hydrogen bonding interactions in the molecules blocks the anti-parallel arrangements and shows second order NLO properties in the bulk, in spite of the fact that chromophores 2 and 4 crystallize in the centrosymmetric space group. The first hyperpolarizabilities (β) [β = 56.5 × 10−30 esu (2); β = 81.5 × 10−30 esu (4)] were measured using the hyper Rayleigh scattering (HRS) technique. Chromophore 4 shows enhanced second-order NLO response compared to the other chromophores, due to an extra phenyl group in the molecule creating more planarity and enhancing the conduction of charges, which happens within a molecule (ICT process), between the ferrocene and acceptor groups (–CN and –NO2). The experimental results were corroborated using DFT calculations that comprise functionals like LC-BLYP, CAM-B3LYP and B3LYP and the 6-31+G** level of theory. [ABSTRACT FROM AUTHOR]

A series of 4-ferrcenylbutyl carboxylate esters with different alkyl chain length (C2-C4) of carboxylic acids were synthesized using Fe3O4@SiO2@(CH2)3-Im-bisEthylFc[I] nanoparticles as catalyst and have been characterized with FT-IR, 1H NMR, and 13C NMR. Ferrocenyl-based esters were used as corrosion inhibitors of mild steel in the 1M HCl solution as corrosive media. The corrosion inhibition efficiency of the synthesized ferrocenyl-based esters has been assessed by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The 4-ferrocenylbutyl propionate showed a more effective corrosion inhibition behavior among the studied esters with 96% efficiency after immersion in the corrosive media for 2 weeks. The corrosion inhibition mechanism is dominated by formation of passive layer of inhibitor on the surface of the mild steel by adsorption. Moreover, the adsorption characteristics of 4-butylferrcenyl carboxylate esters on mild steel were thoroughly explored using density functional theory calculations. It was found that the Fe atoms located around the C impurity in the mild steel are the most efficient and active sites to adsorb 4-butylferrcenyl carboxylate esters. [ABSTRACT FROM AUTHOR]

Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6‐tetramethylpiperidide), s‐block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition metal amides lack sufficient basicity to activate these substrates. Breaking new ground in this field, here we present the synthesis and full characterisation of earth‐abundant transition metals M(TMP)2 (M=Fe, Co). Uncovering a new reactivity profile towards fluoroarenes, these amide complexes can promote direct M−H exchange processes regioselectively using one or two of their basic amide arms. Remarkably, even when using a perfluorinated substrate, selective C‐H metalation occurs leaving C−F bonds intact. Their kinetic basicity can be boosted by LiCl or NBu4Cl additives which enables formation of kinetically activated ate species. Combining spectroscopic and structural studies with DFT calculations, mechanistic insights have been gained on how these low polarity metalation processes take place. M(TMP)2 can also be used to access ferrocene and cobaltocene by direct deprotonation of cyclopentadiene and undergo efficient CO2 insertion of both amide groups under mild reaction conditions. [ABSTRACT FROM AUTHOR]

The direct palladium‐catalyzed C−H arylation of 1,3,4‐oxadiazoles with challenging aryl chloride substrates is promoted by the use of a specifically designed electron‐rich ferrocenyl diphosphane. This protocol employs 0.5 to 1.0 mol % catalyst loading without any additives such as copper or ammonium salts, and equally tolerates electron‐donating and electron‐withdrawing substituents on the (heteroaryl)aryl halides, as illustrated by the efficient synthesis in 86 % yield of the anti‐tubercular agent PHOXPY (2‐(5‐phenyl‐1,3,4‐oxadiazol‐2‐yl)pyrazine) by a late‐stage arylation using 2‐chloropyrazine. [ABSTRACT FROM AUTHOR]

Minireview describes recent (2014–2024) advances in the synthesis of five- to seven-membered azaheterocycles using heteroannulation of monosubstituted ferrocenes. Most of the methods described here are based on asymmetric transition metal catalysis. [ABSTRACT FROM AUTHOR]

Desalination is considered a promising solution to alleviate water shortages, yet current methods are often restricted, due to challenges like high energy consumption, significant cost, or limited desalination capacity. In this study, we present a novel approach of redox flow desalination (RFD) utilizing the highly aqueous-soluble and reversible redox-active compound, potassium 1,1′-bis(sulfonate) ferrocene (1,1′-FcDS). This water-soluble organic compound yielded stable and rapid desalination, sustaining extended operation without notable decay and achieving an impressive desalination rate of up to 457.5 mmol·h−1·m−2 and energy consumption as low as 40.2 kJ·molNaCl−1. Specifically, the RFD device effectively desalinated a 50 mM NaCl solution to potable standards within 6000 s using 1,1′-FcDS. It maintained an average energy consumption of 178.16 kJ·molNaCl−1 and exhibited negligible deterioration in desalination rate, energy efficiency, and charge efficiency throughout a rigorous 12,000 s cycling test. Furthermore, the versatility of this method was demonstrated by effectively treating saline water with varying initial concentrations from 10 mM to 50 mM, showcasing its potential across a broad spectrum of applications. [ABSTRACT FROM AUTHOR]

Tailoring of organometallics structure toward desirable properties continues to be both fascinating and challenging in the field of materials science. Herein, a novel ferrocene derivative with long straight‐chain alkane mono‐substituent is synthesized and used as multifunctional organometallic additive in the base oil. This ferrocene‐based organometallic compound (MFc) is synthesized via the Friedel‐Crafts acylation of ferrocene with myristyl chloride, followed by reduction with sodium borohydride. The chemical structure, crystallizability, surface morphology, and the thermal properties of the as‐synthesized compound are systematically characterized. As the iron‐containing standard substance, the MFc was preferable dissolve in lubricating oil with the iron element content as high as 2*105 ppm. Resultantly, the MFc/oil solutions exhibited excellent stability even after high‐speed centrifugal treatment, long‐term storage up to 3 months, and ultra‐low temperature treatment at −40°C for 24 h. Moreover, the MFc as a functional lubricant additive could reduce the average wear scar diameter, wear volume, and coefficient of friction with 40%, 73%, and 18%, respectively, as compared to the corresponding pure base oil. This synthetic strategy provides a novel perspective for the design of functional organometallics, and the as‐synthesized novel ferrocene derivative may find a wide range of advanced potential applications in analytical chemistry, tribology, and interfacial science. [ABSTRACT FROM AUTHOR]

Two series of new ferrocenyl pyrazolines have been synthesized by the reaction of ferrocenyl chalcones and their analogues with hydrazine hydrate in the presence of corresponding carboxylic acid. Single‐crystal X‐ray crystallographic data were used for detailed analysis of the interesting versatility of four compounds in the formation of intermolecular interactions. The analysis revealed an excellent structural flexibility of the present ferrocenyl pyrazoline molecules for the non‐covalent interactions, with a particular contribution of the ferrocene units. In addition, for comparison with crystallographic findings, we investigated the protective effect of all compounds on DNA against hydroxyl and peroxyl radicals induced by Fe2+, H2O2, and 2,2′‐azobis(2‐amidinopropane) dihydrochloride (AAPH). The results indicated that all compounds showed rather similar DNA protective activity, which was comparable with quercetin as a well‐known protective compound. This similarity in antigenotoxic action could be explained by the established excellent structural flexibility of ferrocenyl pyrazolines for the formation of different intermolecular interactions as important structural property for molecular recognition. [ABSTRACT FROM AUTHOR]

The convenient method for the synthesis of α‐([sydnon‐ and sydnone imin]‐4‐yl‐thio)acetylferrocenes was elaborated. A growth‐regulating activity of these ferrocene derivatives as well as their antidote activity against Metsulfuron‐Methyl (Zinger WP) herbicide was investigated in vegetation experiments on corn seedlings. The high dose‐dependent growth regulating activity of a number of the ferrocenes bearing a mesoionic heterocyclic substituent (sydnone or sydnone imine) was discovered. [ABSTRACT FROM AUTHOR]

This study investigates the potential use of ferrocenyl‐substituted porphyrins as organic electrode materials for sodium secondary batteries. Expressly, 5,15‐di(ferrocenyl)‐10,20‐di(pentafluorophenyl)porphyrins (free base, Fc−H2Por), along with its zinc (Zn[II] complex, Fc−ZnPor) and nickel (Ni[II] complex, Fc−NiPor) derivatives were synthesized and employed as the electrode materials. The charge‐discharge processes disclosed that the ferrocenyl‐substituted porphyrin compound performs electrochemical processes poorly without chelating metals. In contrast, when the ferrocenyl‐substituted porphyrins were metalated with Ni(II) and Zn(II), they exhibited dual ionic charge‐discharge capabilities, indicating their stable electrochemical properties. In particular, long‐term cycle tests emphasized the superior stability and high Coulombic efficiency of Fc−ZnPor electrodes. Computational calculations provided conclusive evidence of variances in aromatic stabilization energy based on the metal center, significantly influencing the chemical stability and electrochemical performance. These findings can deliver valuable insight for further development and optimizations in energy storage applications. [ABSTRACT FROM AUTHOR]

Simple and reliable electrochemical sensors are highly demanded in medicine and pharmacy for the fast determination of metabolites and biomarkers of diseases. In this work, a flow-through biosensor system was developed on the base of a screen-printed carbon electrode modified with pillar[3]arene[2]quinone and ferrocene implemented in carbon black. The modification was performed in a single step and resulted in the formation of a stable layer with good operation characteristics. Uricase was immobilized on the inner walls of a replaceable reactor by carbodiimide binding. A flow-through cell was manufactured by 3D printing from poly(lactic acid). The flow-through system was first optimized on the hydrogen peroxide assay and then used for the determination of 1 nM–0.1 mM uric acid (limit of detection 0.3 nM, 20 measurements per hour). Implementation of ferrocene resulted in a synergetic increase in the cathodic current of H2O2 reduction measured by flow switching in chronoamperometric mode. The developed system was tested on the determination of uric acid in artificial urine and Ringer–Locke solution and showed a recovery rate of 96–112%. In addition, the possibility of determination of H2O2 in commercial disinfectants was shown. Easy assembly, fast and reliable signal and low consumption of the reagents make the system developed attractive for routine clinical analysis of metabolites. [ABSTRACT FROM AUTHOR]

The chiral P,N,N‐ligands represented a new type of tridentate ligand developed in recent years and displayed wide utilities in asymmetric catalysis. In the past decades, numerous chiral P,N,N‐ligands with ferrocene, phenethylamine and spiro backbones were synthesized by addition of an aminopyridine, imidazole or diamines coordinating group. These chiral tridentate P,N,N‐ligands showed excellent performance in the ruthenium, iridium, manganese, or cobalt‐catalyzed asymmetric hydrogenations. A wide range of substrates, including simple ketones, α‐halogenated ketones, α‐hydroxy ketones, α‐ or β‐amino keto‐ ones, α‐, γ‐, or δ‐keto acids, α‐ or β‐keto amides, β‐ or δ‐keto esters, α‐ or β‐enones, olefins, imines, quinolines and indoles, could be hydrogenated to afford the corresponding chiral products with high yields and enantioselectivities. In this review, progress on the asymmetric hydrogenation of C=O, C=N, C=C bonds with chiral tridentate P,N,N‐ligands was summarized. [ABSTRACT FROM AUTHOR]

Hybrid phosphines usually combine a phosphine moiety with another heteroatom secondary donor group in their structures while compounds equipped with hydrocarbyl π–donor moieties remain uncommon. This contribution reports the synthesis and structural characterization of the first P/π-allyl-chelating complexes that were obtained using the structurally flexible and redox-active ferrocene unit as the scaffold, viz. [PdCl(R2PfcCHCHCH2-η3:κP)] (1R; R = Ph and cyclohexyl (Cy); fc = ferrocene-1,1′-diyl). These compounds were synthesized from the respective phosphinoferrocene carboxaldehydes R2PfcCHO via reaction with vinylmagnesium bromide to generate 1-(phosphinoferrocenyl)allyl alcohols, which were subsequently acetylated. The resulting allyl acetates reacted smoothly with [Pd2(dba)3]/[Et3NH]Cl (dba = dibenzylideneacetone) to produce the target compounds. Complexes 1R and their nontethered analogues [PdCl(η3-C3H5)(FcPR2-κP)] (5R; Fc = ferrocenyl) were evaluated as pre-catalysts for the Pd-catalysed allylic amination of cinnamyl acetate with aliphatic amines and Suzuki–Miyaura-type cross-coupling of 4-tolylboronic acid with benzoyl chloride. In these reactions, better results were achieved with compounds 5R (particularly with 5Ph), presumably because they form more stable LPd(0)-type catalysts. [ABSTRACT FROM AUTHOR]

The versatile properties of bipolar organic electrode materials have attracted considerable attention in the field of electrochemical energy storage (EES). However, their practical application is hindered by their inherent limitations including low intrinsic electrical conductivity, low specific capacity, and high solubility. Herein, a bipolar organic molecule combining both porphyrin and ferrocene moieties (CuDEFcP) [5,15‐bis(ethynyl)‐10,20‐di ferrocenyl porphinato]copper(II)) has been developed. It is proposed as a new organic electrode material with multifunctional application for rechargeable organic lithium‐based batteries (ROLBs) and dual‐ion organic symmetric batteries (SDIBs). Superior performance was delivered as cathode material in lithium based dual‐ion batteries (LDIBs), with a high initial discharge capacity of 300 mAh. g−1 at 0.2 A. g−1 and a reversible capacity of 58 mAh. g−1 after 5000 cycles at 1 A. g−1. However, employing it as an anode material in lithium‐ion batteries (LIBs), a reversible capacity of 295 mAh. g−1 at 0.2 A. g−1 was delivered. In SDIBs, in which CuDEFcP is used as both anode and cathode, an average discharge voltage of 2.4 V and an energy density of 261 Wh.kg−1 were achieved. [ABSTRACT FROM AUTHOR]

Specific features of thermal transformations of ferrocene Fe(C5H5)2 at a pressure of 10 GPa upon laser heating to 2200 K have been investigated in diamond anvil cells. Maps of the temperature distribution on the sample during the heating have been obtained. The structure and properties of the transformation products have been studied by X-ray diffraction analysis, transmission electron microscopy, and Mössbauer spectroscopy. It is established that a characteristic feature of ferrocene transformations upon laser heating is the simultaneous formation of nanoparticles of iron (α-Fe) and iron carbide (Fe7C3) crystalline phases. The presence of α-Fe in the products of thermal transformations of ferrocene at high pressures has been observed for the first time. Possible mechanisms of the simultaneous formation of these nanoparticles during ferrocene transformations are discussed. [ABSTRACT FROM AUTHOR]

The addition of Na[BArF24] (BArF24 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) to [Pd(PP)Cl2] (PP = 1,1′-bis(phosphino)ferrocene ligands) compounds results in the loss of a chloride ligand and the formation of the dimeric species [Pd2(PP)2(μ-Cl)2][BArF24]2. In most cases, the addition of a monodentate phosphine, PR3, to these dimeric species leads to cleaving of the dimer and formation of [Pd(PP)(PR3)Cl][BArF24]. While these reactions are readily observed via a significant color change, the 31P{1H} NMR spectra offer more significant support, as the singlet for the dimer is replaced with three doublets of doublets. The reaction seems to take place for a wide range of PR3 ligands, although there do appear to be steric limitations to the reaction. The compounds were thoroughly characterized by NMR, and X-ray crystal structures of several of the compounds were obtained. In addition, the ferrocenyl backbone of the 1,1′-bis(phosphino)ferrocene ligands provides an opportunity to examine the oxidative electrochemistry of these compounds. In general, the potential at which oxidations of these compounds occurs shows a dependence on the phosphine substituents. [ABSTRACT FROM AUTHOR]

Bis(2‐picolyl)amine (bpa), iminodiacetamide (imda), and bis‐1,2,3‐triazole (bta) ferrocene ligands (L) with and without an aliphatic linker were prepared by multi‐step synthesis. The cis‐fac, trans‐fac, or mer stereochemistry of their ML2 complexes with Ni(II), Cu(II), Cd(II), and Zn(II) was studied in the solid state (infrared [IR] and single‐crystal X‐ray diffraction [SC‐XRD]), in solution (nuclear magnetic resonance [NMR] and cyclic voltammetry [CV]) and by density functional theory (DFT) calculations. Crystal structures were determined for bpa ligand 7, and complexes [Ni(1)2](NO3)2 (1Ni), [Cu(8)2]OTf2 (8Cu), [Ni(10b)2](NO3)2 (10bNi), and [Cu(10b)2]OTf2 (10bCu). The bond strength of the central metal ion to the ligand amine nitrogen atom was studied by NMR, electrochemistry, and DFT. The information on redox‐active centers, electron transfer properties of ferrocene ligands (L), and their in situ complexation with zinc(II) and nickel(II) ions were obtained by voltammetric analysis. In addition, DFT calculations showed that the electron ionization in ML2 complexes occurs from one of the ferrocene units, leaving the electronic structure of the other ligand intact, while some of the expelled electron density is recovered by the adjacent amine through resonance. This effect is more pronounced in the free ligands, because the eventual amine resonance in ML2 needs to balance its Zn(II) coordination participation, which justifies why they show higher ionization energies over free ligands. Moreover, due to lower steric hindrance, the N(amino)–Zn(II) coordination is additionally stronger in 1:1 ML complexes, which makes their electron depletion further more demanding. If compared with the clinical drug cisplatin, complexes of bpa 1Ni and imda 2Ni showed a better effect on the viability of different tumor cell lines and better selectivity towards normal cells. Treatment with 1Ni and 2Ni causes an increase of cells in the S phase of the cell cycle and leads to the accumulation of cells in G0/G1. A decrease in the expression level of anti‐apoptotic marker Bcl‐2 upon treatment with both compounds together with increased amount of Annexin V‐FITC positive cells implied apoptosis as the mode of cell death. [ABSTRACT FROM AUTHOR]

Acylated N‐acetyl hexosamine hemiacetals are known for their cytotoxicity. We have previously reported that cytotoxicity can be increased by replacing one or more acyloxy groups with fluorine. Herein, we present the synthesis of 4,6‐difluorinated d‐gluco‐ and 4‐fluorinated d‐galacto‐configured hexosamine‐derived glycoconjugates with organoruthenium or ferrocene complexes and their in vitro cytotoxicity against three cancer cell lines (A2780, SK‐OV‐3, and MDA‐MB‐231) and one noncancerous cell line (HEK‐293). The attachment of the organometallic moiety at the 2‐position significantly enhanced the cytotoxicity, especially against triple‐negative MDA‐MB‐231 and the cisplatin resistant SK‐OV‐3 cancer cells. We observed a clear significance of an unprotected and acetyl protected anomeric hydroxyl for the cytotoxicity. Glycoconjugates with a non‐hydrolysable organic or organometallic group at the anomeric position were generally nontoxic. A more detailed analysis revealed that, in particular, complexes with the ruthenium tetrazene complex induced apoptosis in both SK‐OV‐3 and MDA‐MB‐231 cells, as demonstrated by western blot analysis and Annexin V‐FITC/PI staining. The structures of the two most cytotoxic organoruthenium and ferrocene glycoconjugates were confirmed by X‐ray diffraction analysis. [ABSTRACT FROM AUTHOR]

Three complexes containing diosmium(I) sawhorse units have been synthesized by reactions of 1,1'-bis(diphenylphosphino)ferrocene (dppf) with [Os2(µ-acetate)2(CO)6], [Os2(µ-acetate)2(CO)4(κ1-dppf)2] (1), [(µ-dppf){Os2(µ-acetate)2(CO)4(κ1-dppf)}2] (2), and [(µ-dppf)3{Os2(µ-acetate)2(CO)4}3] (3). In all three cases, the axial CO ligands of the diosmium starting material were replaced by axial dppf ligands. Both 1 and 2 contain two monodentate dppf ligands. In each molecule of 2, there is also one bidentate dppf ligand that serves as a bridge between two Os2 sawhorse units. Complex 3 has a unique cyclic molecular structure involving three sawhorse units connected by three bidentate bridging dppf ligands with alternating sawhorse and dppf moieties forming a ring. Complexes 2 and 3 were characterized by X-ray crystallography. [ABSTRACT FROM AUTHOR]

Quasi‐two‐dimensional (Quasi2D) perovskite materials gained widespread attention due to whose unique and highly desirable luminescence properties. However, the behavior of perovskite lightemitting diodes (PeLEDs) is prejudiced by inefficient cascading energy transfer of perovskite film and unbalanced charges injection. Here, ferrocene carboxylic acid (FcAd) is employed between hole transport layer (HTL) and perovskite layer as a molecular bridge to solve the current problems of PeLEDs. Ferrocene units can bond with [PbBr6]4−, forming one‐dimensional (1D) intermediate phases of FcPbBr3 at the interface, which can manipulate the growth kinetics of perovskite and reconstruct the phase distribution. Therefore, due to the suppression of low dimensional phase content, not only is the cascaded energy transfer of PEA2(CsPbBr3)2PbBr4 films effectively achieved, but also the quasi‐2D perovskite's work function is reduced. Additionally, Pb2+ coordinated with the carboxyl group of FcAd, inducing an electric dipole effect that leads to an further upward shift of the perovskite energy level. Eventually, the synergy achieves a significant tailoring between the perovskite and HTL energy exhibits the most excellent external quantum efficiency (EQE) exceeds 27% and optimal brightness exceeds 240000 cd m−2. Therefore, the preparation method will provide an effective strategy to widen the color gamut of next‐generation displays. [ABSTRACT FROM AUTHOR]

The development of turn-based inhibitors of protein–protein interactions has attracted considerable attention in medicinal chemistry. Our group has synthesized a series of peptides derived from an amino-functionalized ferrocene to investigate their potential to mimic protein turn structures. Detailed DFT and spectroscopic studies (IR, NMR, CD) have shown that, for peptides, the backbone chirality and bulkiness of the amino acid side chains determine the hydrogen-bond pattern, allowing tuning of the size of the preferred hydrogen-bonded ring in turn-folded structures. However, their biological potential is more dependent on their lipophilicity. In addition, our pioneering work on the chiroptical properties of aminoferrocene-containing peptides enables the correlation of their geometry with the sign of the CD signal in the absorption region of the ferrocene chromophore. These studies have opened up the possibility of using aminoferrocene and its derivatives as chirooptical probes for the determination of various chirality elements, such as the central chirality of amino acids and the helicity of peptide sequences. [ABSTRACT FROM AUTHOR]

Mild‐heat photothermal antibacterial therapy avoids heat‐induced damage to normal tissues but causes bacterial tolerance. The use of photothermal therapy in synergy with chemodynamic therapy is expected to address this issue. Herein, two pseudo‐conjugated polymers PM123 with photothermal units and PFc with ferrocene (Fc) units are designed to co‐assemble with DSPE‐mPEG2000 into nanoparticle NPM123/Fc. NPM123/Fc under 1064 nm laser irradiation (NPM123/Fc+NIR‐II) generates mild heat and additionally more toxic ∙OH from endogenous H2O2, displaying a strong synergistic photothermal and chemodynamic effect. NPM123/Fc+NIR‐II gives >90% inhibition rates against MDR ESKAPE pathogens in vitro. Metabolomics analysis unveils that NPM123/Fc+NIR‐II induces bacterial metabolic dysregulation including inhibited nucleic acid synthesis, disordered energy metabolism, enhanced oxidative stress, and elevated DNA damage. Further, NPM123/Fc+NIR‐II possesses >90% bacteriostatic rates at infected wounds in mice, resulting in almost full recovery of infected wounds. Immunodetection and transcriptomics assays disclose that the therapeutic effect is mainly dependent on the inhibition of inflammatory reactions and the promotion of wound healing. What is more, thioketal bonds in NPM123/Fc are susceptible to ROS, making it degradable with highly favorable biosafety in vitro and in vivo. NPM123/Fc+NIR‐II with a unique synergistic antibacterial strategy would be much less prone to select bacterial resistance and represent a promising antibiotics‐alternative anti‐infective measure. [ABSTRACT FROM AUTHOR]

A biradical formed by coordination of the organogold derivative of a nitronyl nitroxide radical with 1,1′-bis(diphenylphosphino)ferrocene was obtained. According to X-ray diffraction data, the Au—Au distance in the biradical structure is short (3.372 Å). The O atoms of paramagnetic groups form short intramolecular contacts with H atoms of cyclopentadienyl anions (2.360 and 2.581 Å) and with methyl H atoms (2.280 and 2.525 Å), as well as intermolecular contacts with H atoms of methyl groups (2.462 and 2.610 Å). Using cyclic voltammetry, it was established that the oxidation of the biradical occurs reversibly in three stages at potentials equal to −34, 232, and 845 mV vs. Ag/AgCl. Density functional calculations and the QTAIM and NBO analyses revealed that there is a weak noncovalent bond between gold atoms in the biradical complex due to partial transfer of an electron from the 5d orbital of one AuI ion to the 6s orbital of the other AuI ion. A weak intramolecular antiferromagnetic exchange interaction (J/kB ≈ −20 K) in the crystal structure was predicted. [ABSTRACT FROM AUTHOR]