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Addition of two equivalents of NaS2CNHBz to CuSO4 affords the yellow diamagnetic coordination polymer [Cu(S2CNHBz)]n (1), resulting from intramolecular electron-transfer and concomitant formation of the thiourea, (BzNH)2C＝S. 1 reacts with PPh3 and 1,1′-bis(diphenylphosphino)ferrocene (dppf) in CH2Cl2 to give monomeric [Cu(κ2-S2CNHBz)(PPh3)2] (2) and [Cu(κ2-S2CNHBz)(κ2-dppf)] (3), respectively, both of which have been crystallographically characterised. While 1 is thermally stable in dimethylsulfoxide (DMSO) up to ca. 70 °C, addition of nBuNH2 to 1 leads to its rapid decomposition to afford CuS (covellite) nanomaterials; indeed in neat nBuNH2, covellite formation is rapid at room temperature. Thus, 1 serves as an effective low-temperature base-induced single source precursor to covellite nanomaterials. [ABSTRACT FROM AUTHOR]

Addition of two equivalents of NaS2CNHBz to CuSO4 affords the yellow diamagnetic coordination polymer [Cu(S2CNHBz)]n (1), resulting from intramolecular electron-transfer and concomitant formation of the thiourea, (BzNH)2C＝S. 1 reacts with PPh3 and 1,1′-bis(diphenylphosphino)ferrocene (dppf) in CH2Cl2 to give monomeric [Cu(κ2-S2CNHBz)(PPh3)2] (2) and [Cu(κ2-S2CNHBz)(κ2-dppf)] (3), respectively, both of which have been crystallographically characterised. While 1 is thermally stable in dimethylsulfoxide (DMSO) up to ca. 70 °C, addition of nBuNH2 to 1 leads to its rapid decomposition to afford CuS (covellite) nanomaterials; indeed in neat nBuNH2, covellite formation is rapid at room temperature. Thus, 1 serves as an effective low-temperature base-induced single source precursor to covellite nanomaterials. [ABSTRACT FROM AUTHOR]

Molecular imprinting is an advanced technology in the fabrication of novel chemical sensors recently applied, enabling rapid responses and highly selective binding to specific molecules, thereby enabling efficient detection of material constituents. In this study, a new molecularly imprinted electrochemical sensor (MIES) utilizing ferrocene‐functionalized carbon‐nanotubes (Fc‐CNTs) was developed for the determination of tryptophan (Trp). The formation of molecularly imprinted polymer (MIP) involves polymerization in dimethyl sulfoxide (DMSO) using Trp, methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) as the template molecules, functional monomers, and cross‐linking agents, respectively. Due to the modification of MIPs, the sensor achieves high performance. The sensor demonstrates a linear range from 1 to 45 μM and from 45 to 330 μM, with the limit of detection of 0.44 μM, exceeding that of the majority of sensors reported in the literature. Furthermore, the sensor can effectively detect Trp in real samples, including human serum and amino acid oral liquid. The recovery rate of Trp in human serum samples is 94.2 % to 105.30 %, and in amino acid oral liquid is 94.3 % to 101.68 %. This study provides a promising approach for the effective detection and analysis of tryptophan constituents. [ABSTRACT FROM AUTHOR]

Using (bis)diethoxyphosphoryl ferrocene [Fc(O＝P(OEt)2)2] and transition metal carboxylates – [M2(μ-OOCR)4(CH3CN)2], M = CuII, R = tBu, (C5H4)Mn(CO)3 (Cym) or [M3(μ-OOCR)6(CH3CN)2], M = NiII, CoII, R = Cym, a series of heterometallic polymers with metal cores {Cu2Fe}n (1), {Cu2Mn4Fe}n (2) {Ni2Mn4Fe}n (3), and {Co2Mn4Fe}n (4) were obtained under mild conditions. Compounds 1 and 2 showed antibacterial activity against a Mycobacterium smegmatis strain in vitro. [ABSTRACT FROM AUTHOR]

The document is the contents list for the journal "Chemical Communications" published in 2024. It includes various articles on topics such as precision photodynamic therapy, materials design for polymers, efficient electrocatalysts, and molecular perovskites. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document provides a comprehensive overview of the articles included in the journal issue. [Extracted from the article]

It has been known since the 1990s that the introduction of a ferrocenyl–type substituent into compounds with proven biological activity can improve their properties. More recently, it was also shown that a carbon bridge connecting the two cyclopentadienyl rings in ferrocene derivatives could enhance the biological properties of the new compounds compared to those without them. However, the synthesis of ferrocenes with this additional linker, known as ansa–ferrocenes, is more difficult due to advanced synthetic protocols and the phenomenon of planar chirality in ring–substituted compounds. As a result, research into the formation of hybrids, conjugates and other ansa–ferrocene derivatives has not been widely conducted. This review discusses the potential biological properties of these units, covering scientific articles published between 1980 and 2024. [ABSTRACT FROM AUTHOR]

ABSTRACT A new 1,2,3‐triazole functionalized ferrocene (1,2,3‐TAFc) produced by Cu(I)‐catalyzed click reaction was investigated as positive electrolyte for aqueous organic flow batteries (AOFBs). The molecule is highly soluble in 1 M hydrochloric acid and displays high electrochemical reversibility. 1,2,3‐TAFc demonstrated good stability during cycling with a low capacity decay (0.011%/cyc, 3.0%/day) and high Coulombic efficiency (99.4%) over 280 cycles when tested in a flow battery at low concentration. This low capacity decay was attributed to the instability of ferrocene. These findings indicate that a stable and water‐soluble catholyte for AOFBs can be obtained with structural modifications of 1,2,3‐TAFc. [ABSTRACT FROM AUTHOR]

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]

Since its discovery in the early 1950s, the sandwich‐type structure of ferrocene has sparked significant research into its applications across various disciplines, including asymmetric synthesis, medicinal chemistry, and materials science. Planar chiral ferrocenes play a crucial role in asymmetric catalysis by serving as essential scaffolds for chiral ligands and catalysts. Classical methods for synthesizing planar chiral ferrocenes often encounter limitations such as low atom economy and lengthy synthesis steps. In contrast, catalytic desymmetrization synthesis strategies offer a promising alternative due to their ability to enhance step and atom efficiency. This review highlights recent advancements in this field, particularly focusing on transition‐metal‐catalyzed C−H functionalization and catalytic enantioselective desymmetrization reactions. [ABSTRACT FROM AUTHOR]

ABSTRACT A practical and straightforward strategy for the synthesis of ferrocene appended furopyranone, furochromenone, and benzofuranone via a metal‐free annulation reaction of imidazolium ylide with enone mediated by saccharin‐based ionic liquid has been reported. The mechanistic studies show an approach through synergistic dual activation of enone and imidazolium ylide via cation and anion of ionic liquid, respectively. This operationally simple protocol offers an easy and rapid access to a library of ferrocene appended furopyranone, furochromenone, and benzofuranone in moderate to good yields through the involvement of a six‐membered transition state. [ABSTRACT FROM AUTHOR]

Although there have been numerous great field emission reports of pure and hybrid carbon nanotubes (CNTs) with ultra‐low turn‐on field and ultra‐high emission stability, practically all of the reports indicate concern about CNT manufacture on a large scale. This is due to the fact that CNT experiments require high pressure, temperature, metal catalysis, and an inert environment, and even after meeting all of these perfect conditions, the yield is quite low. Furthermore, as CNT is relatively inert in nature, it is nearly hard to make it reactive with any other metal without adequate functionalization. Keeping this in mind, this work reports the synthesis of CNT in amorphous form by a simple low‐temperature solid‐state reaction between ammonium chloride and ferrocene. The as‐synthesized CNT is further functionalized by silver oxide nanoparticle without additional functionalization. X‐ray diffraction (XRD) confirms the proper phase formation as well as the successful functionalization of the pure and hybrid sample, electron microscopic images confirm the successful functionalization of the as‐prepared CNT whereas Fourier transformed infrared (FTIR) spectroscopic analysis gives the ideas about different bonding present in all the samples. It has been found that the hybrid sample gives much better field emission performance compare to the pure CNT with betterment in both turn‐on field and enhancement factor more than 100%. The betterment is believed to be due to the favorable band bending, larger number of emission sites, and sharp curvature of the silver particles. [ABSTRACT FROM AUTHOR]

ABSTRACT Trypanosomatids are the etiologic agents of numerous parasitic diseases that cause significant morbidity and mortality in millions of people and animals around the world. Approved antitrypanosomatid agents are limited by several drawbacks, such as severe toxicity, lengthy treatment, need for hospitalization, and susceptibility to drug resistance. Consequently, parasitic diseases remain a substantial public health problem, and new drugs are required, especially drugs suitable for rural health systems that have limited resources. In an attempt to find antitrypanosomatid agents to address this problem, we report here on the synthesis and biological efficacy of ferrocene derivatives of nifuroxazide and nitrofurazone, which were designed by replacing the nitrofuran scaffold within their structures with the ferrocene moiety. The 1,2‐disubstituted ferrocene intermediates 8 and 9, featuring amine and carboxaldehyde groups, exhibited the best in vitro antiamastigote activity against Leishmania major strain NIH S and Leishmania donovani strain 9515, respectively. Ferroxazide derivative 15 was revealed as a mammalian cell nontoxic hit compound against Trypanosoma congolense strain IL3000 trypomastigotes; however, no in vivo treatment efficacy was observed against T. congolense strain IL3000‐infected BALB/c mice during a preliminary animal study. The synthesized ferrocene derivatives were poorly soluble in the in vitro and in vivo testing media, hindering uniform sampling and dosing. This study's outcome indicates that replacing the 5‐nitrofuran moiety with ferrocene did not increase antitrypanosomatid activity compared to the nitrofuran parent drugs nifuroxazide and nitrofurazone. [ABSTRACT FROM AUTHOR]

[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]

Functionalized ferrocene derivatives have a wide range of applications across various scientific fields. Although significant progress has been made in synthesizing 1,2‐disubstituted ferrocene derivatives, the preparation of 1,3‐disubstituted ferrocenes remains challenging. Recently, however, several powerful synthetic approaches to 1,3‐disubstituted ferrocenes have been reported. This review aims to present the evolution of these synthetic methods, from initial stoichiometric approaches to the more recent catalytic methodologies. [ABSTRACT FROM AUTHOR]

The paper presents a method of microwave influence on ferrocene C10H10Fe and graphite to obtain multilayer carbon nanotubes (MWCNTs)—designed to improve the electrical and thermophysical properties of Organosilicon elastomer (Silagerm 8020). Diagnostics and characterization of the synthesized MWCNTs were carried out by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. According to SEM data, it follows that the morphology of the synthesized MWCNTs has the form of filamentous formations intertwined in bundles with a diameter of individual MWCNTs from 40 to 60 nm and a length up to several microns. At the same time, the surface of most of the MWCNTs is covered with a continuous layer of iron (Fe). The EDX method also confirmed the Fe and oxygen content on the surface of the MWCNTs. The XRD method identified the presence of Fe in combination with carbon in the form of Fe3C iron carbide and pure Fe iron at 44.7°. The compound Fe3C is also referred to the active phase of Fe allowing the synthesis of MWCNTs. By increasing the concentration of MWCNTs in the elastomer, an increase in thermal conductivity with percolation transition was achieved at a concentration of 8% MWCNTs. The maximum thermal conductivity of the nanomodified elastomer was 0.48 W/(m °C), which corresponded to the mass concentration of MWCNTs equal to 8 wt %. At the same time, the electrical conductivity of the composite, when the MWCNT concentration was changed from 1 to 8%, increased in the range from 4 × 10–5 to 2.4 S cm–1 and is also due to the percolation of MWCNTs in the elastomer matrix. [ABSTRACT FROM AUTHOR]

Ferrocene‐modified natural compounds are of interest for the development of new pharmaceuticals due to improved bioavailability, increased bioactivity, and also as redox markers or vectors. Betulin is a natural plant‐derived product with a wide range of pharmacological properties. However, it is limited in its bioavailability and efficacy. In order to enhance its pharmacological profile, the ferrocene modification of betulin was used in this study. A hybrid of the betulin core (up to 30 % betulin in birch bark) with a ferrocene moiety combined through a piperazine linker (compound 12) was prepared in good yield from readily available ferrocene carboxylic acid and betulonic acid, a natural betulin derivative, via coupling reactions. Spectroscopic techniques, including 1H and 13C NMR, IR and UV‐vis spectroscopy, as well as circular dichroism (CD), were applied to characterize the physicochemical and chiroptical properties. The cytotoxicity of the synthesized hybrid 12 and its ferrocene precursor 13 on MCF‐7 human cancer cell lines were in vitro evaluated by the MTT assay. The IC50 cytotoxicity index of 12 was found to be 26 μM. The theoretically calculated energies of the HOMO‐LUMO orbitals and electronic characteristics of betulin 10, betulonic acid 11, hybrid 12 and ferrocenyl piperazine 13 were determined by the DFT method with hybrid functionals ωB97XD, LC‐ωPBE and B3LYP‐D3 and pure M06 L functionals, with a 6‐311+G(d), 6‐31G(d) or TZV basis set. [ABSTRACT FROM AUTHOR]

Another class of gold(I) redox‐switchable catalysts, incorporating ferrocenyl phosphane‐imines, enriches the existing library of gold(I) complexes. Our catalyst proves efficacy in gold(I)‐catalyzed cyclizations of furans and benzamides, exhibiting reversible "on‐off" switching. Furthermore, we explored the unconventional role of "Magic Blue", commonly used as an oxidizing agent in various organic transformations, as a potential activator of the Au−Cl bond, initiating conventional gold(I) catalysis. [ABSTRACT FROM AUTHOR]

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]

Recently, redox chemical transformations have been reported to occur spontaneously in microdroplets. The origins of such novel reactivity are still debated, and any systematic correlation of the oxidative/reductive yield with the reactivity of the reactant is yet to be established. Towards this end, we report the simple, outer‐sphere, one‐electron oxidation of a series of ferrocene derivatives spanning a range of oxidation potentials from −0.1 V to +0.8 V vs. Ag/AgCl in acetonitrile microdroplets generated via nebulization and measured by mass spectrometry of the corresponding ferrocenium ions. The reaction environments and dynamics in the droplets are complex, and it is still unclear whether such reactivity correlates with any bulk thermodynamic values. Our key finding is that the ion yields decrease monotonically with the oxidation potential of the ferrocenes, which is a thermodynamic quantity. The ion yields emphatically do not obey the Nernstian ratio, revealing the redox processes in the droplets do not follow the assumptions of bulk steady‐state electrochemistry. Furthermore, oxidative competition in the mixture of several ferrocenes suggest a finite oxidative capacity or oxidant concentration. These results demonstrate that even though ion generation could be an out‐of‐equilibrium and kinetically limited process, the oxidative yield in microdroplets does correlate with thermodynamics, suggesting a possible free energy relationship between the kinetics and thermodynamics of the process. [ABSTRACT FROM AUTHOR]

[Display omitted] Chromatography–mass spectrometry of samples representing the interaction products of ferrocene, radical initiator and monomer taken in the molar ratio of 1:2:10 in toluene solution was used for experimental detection of products indicating the structure and mechanism of formation of metal complex active centers of radical-coordination polymerization. Structures similar to those proposed by the quantum-chemical modeling were demonstrated to be formed with the participation of secondary radicals. [ABSTRACT FROM AUTHOR]

We introduce a novel dual redox mediator synthesized by covalently linking ferrocene dicarboxylic acid (FcDA) and thionine (TH) onto a pre-treated glassy carbon electrode. This unique structure significantly enhances the electro-oxidation of dopamine (DA) and the reduction of hydrogen peroxide (H2O2), offering a sensitive detection method for both analytes. The electrode exhibits exceptional sensitivity, selectivity, and stability, demonstrating potential for practical applications in biosensing. It facilitates rapid electron transfer between the analyte and the electrode surface, detecting H2O2 concentrations ranging from 1.5 to 60 µM with a limit of detection (LoD) of 0.49 µM and DA concentrations from 0.3 to 230 µM with an LoD of 0.07 µM. The electrode's performance was validated through real-sample analyses, yielding satisfactory results. [ABSTRACT FROM AUTHOR]

Two chiral ferrocenylamine alcohols of (R)-[Fe(η5-C5H5){η5-C5H4CH2NHCH(iPr)(CH2OH)}] (1) and (R)-[Fe(η5-C5H5){η5-C5H4CH2NHCH(C6H5)(CH2OH)}] (2) were synthesized by condensation reaction of ferrocenylformaldehyde and chiral aminoalcohols followed by the reduction with sodium borohydride. The crystal structures of the two compounds were determined by single crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic space group P21212 with a = 16.600(8) Å, b = 28.990(14) Å, c = 6.531(3) Å, and Z = 8. Compound 21.13H2O crystallizes in the monoclinic space group I2 with a = 22.671(4) Å, b = 6.2481(10) Å, c = 22.112(4) Å, β = 96.763(12)°, and Z = 8. [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.

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.

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]

Ferrocene is an accidentally discovered organometallic compound that serves as a crucial redox probe in investigating electrochemical charge transfer dynamics. Besides solution phase studies, ferrocene derivatives are well‐explored in molecular thin films, including self‐assembled monolayers on various electrodes for understanding on‐surface redox behavior, molecular electronics, and charge storage applications. Heterogeneous charge transfer is an imperative parameter for efficient charge transport in spin‐dependent electrochemistry, photoelectrochemistry, and molecular electronic devices. In this work, we aim to study the electrochemical charge transfer of ferrocene on various electrodes such as commercially obtained glassy carbon, graphite rod, indium tin oxide (ITO), and as‐prepared gold, and nickel to determine the impact of the nature of the working electrode on the electron transfer rate, diffusion coefficient, and reversibility of the redox process. Both the direct current and alternating current‐based electrochemical experiments are performed, followed by digitization of the experimental results. The kinetics of electron transfer and electrochemical reversibility reveal a strong dependence on the nature of the working electrode, as the electrochemically driven oxidation and reduction of the material of interest are directly related to the Fermi energy and electronic structure of the working electrode. [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]

An approach to the synthesis of derivatives of unsymmetric 1,1′-disubstituted azinylferrocenes containing phenol fragments was proposed. It was found that the introduction of the quinoline or 2,2′-bipyridine moiety increases the E/Z selectivity of the reaction. The monosubstituted acetylferrocene produces the products of the pinacoline rearrangement due to the McMurry coupling, whereas only 1-azinyl-1′-{1-[(4-hydroxyphenyl)-phenylmethylene]ethyl}ferrocenes were formed in the reaction with 1-azinyl-1′-acetyl-ferrocenes. The high antioxidant activity of the synthesized compounds in the ABTS and FRAP assays and high inhibitory activity against self-aggregation of β-amyloid (1–42) was shown. Cytotoxic activity of these compounds was studied on human breast cancer cells (MCF7), non-small-cell lung cancer cells (A549), colorectal cancer cells (DLD-1), and normal dermal fibroblasts (DF-2). [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]

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]

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 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]

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]