Search

Aqueous zinc (Zn) batteries are highly desirable for sustainable and large‐scale electrochemical energy storage technologies. However, the ceaseless dendrite growth and the derived dead Zn are principally responsible for the capacity decay and insufficient lifespan. Here, we propose a dissolved oxygen‐initiated revitalization strategy to reactivate dead Zn via ferrocene redox chemistry, which can be realized by incorporating a trace amount of poly(ethylene glycol) as a solubilizer to improve the solubility of water‐insoluble ferrocene derivatives. Ferrocene scaffold can be spontaneously oxidized to ferricenium cations by dissolved oxygen, which eradicates the dissolved oxygen‐involved Zn corrosion and insulating by‐product generation. Subsequently, the generated ferricenium cations as the scavenger can rejuvenate electrically isolated dead Zn into electroactive Zn2+ ions to compensate the zinc loss. Through this design, the symmetric cell exhibited improved cycle life of 3700 h at 10 mA cm−2, and 220 h under a high depth of discharge of 80 %. Importantly, the Zn||NaV3O8 ⋅ 1.5H2O full cells demonstrated the impressive cycling stability over 1500 cycles at a low N/P ratio of 3.0. This work presents an innovative solution for the revitalization of dead Zn to extend the lifespan of deep‐cycling metal batteries. [ABSTRACT FROM AUTHOR]

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]

Ferrocene (Fc) and Fc derivatives have gained popularity in recent years due to their unique structure and characteristics. Among Fc′s diverse performances, photothermal conversion, as a primary source of energy conversion, has sparked substantial study attention. This Review summaries Fc and Fc derivatives with photothermal characteristics, as well as their applications developed recently. First, methods for the synthesis of Fc‐based materials are systematically discussed. Then, the photothermal conversion mechanism based on nonradiative relaxation is summarized. Furthermore, the most recent advances in Fc‐based materials in photothermal applications are described, including photothermal degradation, photothermal antibacterial, photothermal therapies, photothermal catalysis, solar‐driven water production, and photothermal CO2 separation. Finally, a summary and insights on the photothermal application of Fc‐based materials are provided. This paper seeks to provide researchers with a better knowledge of photothermal behavior while also highlighting the potential of Fc and its derivatives in photothermal fields. [ABSTRACT FROM AUTHOR]

The reaction of the ferrocene derivative Fe(ƞ5-C5H4CO2H)(ƞ5-C5H4CH=CH2) (=fcCO2H) (1) with the zinc reagents [Zn(OAc)2]·xH2O (OAc = acetate; 2a, x = 0; 2b, x = 2) or ZnEt2 (3) in non-aqueous solvents toluene or tetrahydrofuran resulted in the formation of the cluster [Zn4O(fcCO2)6] (4). The structure of 4 in the solid state has been determined by single-crystal X-ray diffraction analysis. Cluster 4 crystallizes in the triclinic space group P 1 ‾ . In 4, the cluster core is set-up by four zinc(II) ions which are forming the vertices of a tetrahedron with a μ4-oxygen atom in its center. Six μ-fcCO2 units bridge the edges of the tetrahedron. IR spectroscopy confirms with ∆νCO2 = 91 cm−1 (∆νCO2 = νCO2,asym − νCO2,sym) the μ-bridging character of the fcCO2 entities. Cyclic voltammetry studies showed a reversible redox event at E°′ = 245 mV versus FcH/FcH+ (FcH = Fe(ƞ5-C5H5)2) for 4 with the six fcCO2 redox events superimposed. High-resolution ESI-TOF measurements verified the identity of 4. [ABSTRACT FROM AUTHOR]

Surfactants are very important compounds that are ubiquitous in biological systems and detergents. Among them, ferrocene surfactants are a very valuable class of stimuli-responsive materials since the presence of ferrocene moiety discloses the chance to control and even modify their amphiphilic properties via a redox-induced change in the surfactant charge. In this paper, we report a new ferrocene-based surfactant: a ferrocene C-3 derivative of cholic acid, a non-classical surfactant. The title compound of this work was meant to show the significant self-assembly behaviour typical of bile salts, improved by the presence of the aromatic ferrocene subunit. We intended to demonstrate that the presence of the redox mediator should provide the derivative with sensitivity to an oxidative stimulus and control over the aggregation properties. The title compound was prepared in two steps from easily accessible precursors, and its optical properties were investigated through UV-Vis absorption spectroscopy. The determination of its critical micellar concentration and redox potential confirmed this derivative's amphiphilic nature and its tendency to be reversibly oxidized. [ABSTRACT FROM AUTHOR]

While the catalytic activation of C–H bonds adjacent to a directing group is well developed in the ferrocene series, the functionalisation of a remote position has scarcely been explored. Here, we summarise the latest developments in this field in the broader context of 1,3-disubstituted ferrocene derivatives. [ABSTRACT FROM AUTHOR]

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]

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]

Ferrocenyl conjugated oxazepine/quinoline derivatives were presented through the reaction of hexadehydro-Diels-Alder (HDDA) generated arynes with ferrocenyl oxazolines under mild conditions via ring-expanding or rearrangement processes. Water molecule participated in this unexpected rearrangement process to produce quinoline skeletons, and DFT calculations supported a ring-expanding and intramolecular hydrogen migration process for the formation of oxazepine derivatives. Two variants of this chemistry, expanded the reactivity between ferrocenyl conjugated substances and arynes, further providing an innovative approach for the synthesis of ferrocene derivatives. [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]

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]

Recently, lead halide perovskites have been developing rapidly in the field of photo-electric functional devices. The key to further enhancing its potential in thin-film photo-electronic devices lies in understanding the charge (electron/hole) separation process and its transfer across the interface. In addition to optimizing the preparation conditions, finding excellent electron/hole transport materials is a matter of priority for improving the efficiency of charge separation between different functional layers in optoelectronic devices. In this work, a novel organic metallic functionalized ferrocenyl acetylacetone (FAAT) derivative was developed as a hole transport material (HTM). The very stable lead halide perovskite material and CsPbBr3 quantum dots are used as carrier donors, and data from TRPL show that the addition of FAAT can improve the carrier separation efficiency at the quantum dot interface by at least 64.6%. Moreover, the excited state dynamics data from transient absorption experiments also show that the excited state dynamics of quantum dots rapidly change from the fluorescence relaxation process (2440 ps) to the hole transfer process (263 ps) after the addition of FAAT. FAAT was used as a dopant-free HTM to improve the photovoltaic performance of the inverted perovskite solar cells (PSCs). As a result, the optimal FAAT-based device efficiency reached 19.05%. All these studies indicate that FAAT is expected to be a cost-effective and chemically stable hole transport material for efficient PSCs. [ABSTRACT FROM AUTHOR]

Ferrocene has a unique structure, i.e., a central iron atom neatly sandwiched between two cyclopentadienyl rings, which has revolutionized the chemists' views about how metals bind to organic π-systems. This structural arrangement leads to some fascinating chemical and photophysical properties. The last three decades, there were reports about receptor molecules that could be considered to perform simple logic operations via coupling ionic bonding or more complex molecular-recognition processes with photonic (fluorescence) signals. In these systems, chemical binding ('input') results in a change in fluorescence intensity ('output') from the receptor. It has been proven that molecules respond to changes in their environment, such as the presence of various ions, neutral species, pHs, temperatures, and viscosities. Since their first realization by de Silva, molecular logic gates have been intensively experimentally studied, with purely theoretical studies being less common. Here, we present the research that has been conducted on Molecular Logic Gates (MLGs) containing ferrocene and their applications. We categorized such systems into three families of MLGs: long-chain molecules (oligomers or polymers) that incorporate ferrocene, medium-sized molecules that incorporate ferrocene, and systems where ferrocene or its derivatives are used as external additives. Furthermore, MLGs including metal cations without the ferrocene moiety are briefly presented, while computational methodologies for an accurate theoretical study of MLG, including metal cations, are suggested. Finally, future perspectives of MLGs containing ferrocene and their applications are also presented. [ABSTRACT FROM AUTHOR]

Ferrocene derivatives show a wide range of pharmacological activities in the medical field, especially in the anti‐tumor field, and can be used as candidate drugs or lead compounds for the treatment of tumors and other diseases. And α‐phenethylamine is an important intermediate for the preparation of fine chemical products. (R)‐(+)‐1‐Phenethylamine ferrocenecarboxylic acid/(S)‐(−)‐1‐phenethylamine ferrocenecarboxylic acid were prepared, named compounds 1 and 2, respectively. Single crystal X‐ray diffraction showed that compounds 1 and 2 crystallized in the orthorhombic system space group P212121, and the crystal structures of compounds 1 and 2 exhibited mirror symmetry. The inhibitory effect of two compounds on SW480, MDA‐MB‐231, and H1299 cells was tested by MTT colorimetry. The IC50 values of the compounds against cancer cells were also calculated. The anti‐cancer effect was more pronounced for compounds in the S‐configuration. Compound 2 made the wild‐type cancer cells undergo apoptosis, thus preventing cancer; it also had the function of helping the cell gene repair defects. [ABSTRACT FROM AUTHOR]

Photo-catalytic CO2 reduction with perovskite quantum dots (QDs) shows potential for solar energy storage, but it encounters challenges due to the intricate multi-electron photoreduction processes and thermodynamic and kinetic obstacles associated with them. This study aimed to improve photo-catalytic performance by addressing surface barriers and utilizing multiple-exciton generation in perovskite QDs. A facile surface engineering method was employed, involving the grafting of ferrocene carboxylic acid (FCA) onto CsPbBr3 (CPB) QDs, to overcome limitations arising from restricted multiple-exciton dissociation and inefficient charge transfer dynamics. Kelvin Probe Force Microscopy and XPS spectral confirmed successfully creating an FCA-modulated microelectric field through the Cs active site, thus facilitating electron transfer, disrupting surface barrier energy, and promoting multi-exciton dissociations. Transient absorption spectroscopy showed enhanced charge transfer and reduced energy barriers, resulting in an impressive CO2-to-CO conversion rate of 132.8 µmol g-1 h-1 with 96.5% selectivity. The CPB-FCA catalyst exhibited four-cycle reusability and 72 h of long-term stability, marking a significant nine-fold improvement compared to pristine CPB (14.4 µmol g-1 h-1). These results provide insights into the influential role of FCA in regulating intramolecular charge transfer, enhancing multi-exciton dissociation, and improving CO2 photoreduction on CPB QDs. Furthermore, these findings offer valuable knowledge for controlling quantum-confined exciton dissociation to enhance CO2 photocatalysis. [ABSTRACT FROM AUTHOR]

In this study, we report a catalyst‐free aminohalogenation process applied to vinylferrocene, employing N‐halosuccinimides (NXS; X=Cl, Br, I) as dual nitrogen and halogen sources. This 1,2‐diheterofunctionalization reaction takes place with complete regioselectivity, wherein the terminal carbon atom of the vinyl group selectively reacts with the electrophilic halogenating reagent, resulting in the formation of a cationic intermediate, which is subsequently captured by the succinimide anion. The structure of the key cationic intermediate was studied using theoretical methods. This intermediate can react with alternative nucleophiles, enabling a three‐component strategy for the synthesis of novel 1,2‐diheterofunctionalized ferrocene derivatives. [ABSTRACT FROM AUTHOR]

The reaction of ferrocene-containing alkenes and alkynes with HSi(OEt)3 and HSiMe(OMe)2 in the presence of Karstedt catalyst (Pt2[(Me2SiCH=CH2)2O]3) was studied. It was found that only terminal alkenes underwent hydrosilylation, while alkynes entered this reaction even in the case of a disubstituted C≡C bond. The synthesized silicon-containing ferrocene derivatives were used as precursors for the preparation of siloxane aerogels, which were characterized by low-temperature nitrogen adsorption, scanning electron microscopy, and Mössbauer spectroscopy. [ABSTRACT FROM AUTHOR]

Two ferrocene derivatives, namely, 1,2-(tetramethylene)-ferrocene and 1,2,1′,2′-bis(tetramethylene)-ferrocene, were synthesized in a four-step reaction sequence starting from ferrocene. Friedel–Crafts acylation of ferrocene using succinic anhydride gave mono- or bis(3-carboxypropinoyl)-ferrocene depending on the stoichiometry of succinic anhydride. The reduction of the keto groups to methylene followed by ring-closing using trifluoroacetic anhydride gave 1,2-(α-ketotetramethylene)-ferrocene or 1,2,1′,2′-bis(α-ketotetramethylene)-ferrocene. The diastereomeric mixture of the latter diketones was separated using column chromatography, characterized via single-crystal X-ray analysis, and assigned its stereochemistry. Reduction of the keto groups to methylene under Clemmensen conditions gave homoannular mono- or bis(tetramethylene)-ferrocene derivatives. The molecular structure of 1,2-(tetramethylene)-ferrocene revealed that the ipso carbon atoms of the cyclopentadienyl group are 0.023(3) Å farther away from Fe(II) compared to the remaining three carbon atoms. Both complexes exhibit lower half-wave oxidation potentials than ferrocene, possibly due to the electron-releasing effects of the tetramethylene bridges. [ABSTRACT FROM AUTHOR]

[Display omitted] The copper-catalyzed azide–alkyne cycloaddition of BODIPY acetylene derivative and ferrocene azides in supercritical CO 2 at 80 °C and 81 bar affords the corresponding triazole-containing BODIPY–ferrocene conjugates in high yields. The fluorescent and electrochemical properties of the compounds thus obtained were explored. [ABSTRACT FROM AUTHOR]

The use of an appropriate preparation route is the key to immobilize active molecules into a host matrix with high loadings and stability. Herein, we demonstrate a simple and general strategy to immobilize ferrocene and its derivatives into ZIF-8 with high loadings of up to 4.3% Fe content. The unique host pore structure allows for the stabilization of guest molecules and effectively prevents their leaching. As a result, the obtained electrocatalysts exhibit competitive oxygen evolution reaction (OER) catalytic performance. Optimized Fc-CHO/ZIF-8 requires only a low overpotential of 238 mV to achieve 10 mA cm−2, along with a relatively small Tafel slope of 44.4 mV dec−1. This performance is superior to that of commercial IrO2, suggesting its potential application in electrochemical energy conversion. [ABSTRACT FROM AUTHOR]

Further improvement of the performance and stability of inverted perovskite solar cells (PSCs) is necessary for commercialization. Here, ferrocene derivative dibenzoylferrocene (DBzFe) is used as an additive to enhance the performance and stability of MA‐ and Br‐ free PSCs. The results show that the introduction of DBzFe not only passivates the defects in the film but also inhibits the ion migration in the film. The final device achieves a power conversion efficiency (PCE) of 23.53%, which is one of the highest efficiencies currently based on self‐assembled monolayers (SAMs). Moreover, it maintains more than 96.4% of the original efficiency when running continuously for 400 h at the maximum power point. [ABSTRACT FROM AUTHOR]

2D conductive Metal–organic frameworks (MOFs) have emerged as promising electrocatalysts. Their unique conjugated structure leads to rapid electron transfer rates and confers excellent electrical conductivity. However, the electrocatalysis environments always involve complicated multiphase interactions. The electrocatalytic efficiencies for 2D MOF are often hampered by low electrical conductivity in solvation and improper adsorption/desorption energy of intermediates, which refers to the electron transfer efficiency between the solid catalysts and solution, as well as the solid catalysts and the gas molecules. In this study, we addressed these limitations by encapsulating guest molecules into the hexagonal nanocavity of 2D MOF. Fc-Ni-HHTP was synthesized by introducing ferrocene derivatives (ferrocene methylamine, Fc-NH2) into Ni-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). It exhibited superior performance in the oxygen evolution reaction (OER) compared to Ni-HHTP, with an overpotential of 482 mV at a current density of 10 mA cm–2, demonstrating excellent electrochemical stability. Density functional theory (DFT) calculations showed that the remarkable electrocatalytic performance of Fc-Ni-HHTP was attributed to the synergistic effect between the ferrocene derivatives and the Ni-HHTP matrix. This work provides a notable way to enhance the electrocatalytic performance of MOFs by introducing a guest molecule into a MOF to improve the multiphase electron transfer rates. [ABSTRACT FROM AUTHOR]

This study investigates novel ferrocene-based electrochemical sensors for metal cation detection via the design, synthesis and characterisation of ferrocene derivatives. Specifically, this research determines the redox potentials of ferrocene versus decamethylferrocene to provide insight into the redox potential variations. The investigation also examines how electrochemical oxidation of the ferrocene moiety can modulate host affinity for transition metal cations via effects such as electrostatic interactions and changes to coordination chemistry. Metal ion coordination to receptors containing functional groups like imine and quinoline is explored to elucidate selectivity mechanisms. These findings advance the fundamental understanding of ferrocene electrochemistry and host–guest interactions, supporting the development of improved cation sensors with optimised recognition properties, sensitivity and selectivity. Overall, this work lays the necessary groundwork for applications in analytical chemistry and sensor technologies via customised ferrocene-derived materials. [ABSTRACT FROM AUTHOR]

Due to increased lipophilicity, stability, and decreased cytotoxicity in biological systems, ferrocene derivatives are promising building blocks for therapeutic agents. This manuscript reports the binding of N'-ferrocenylmethyl-N'-phenylbenzohydrazide (FhD) with deoxyribonucleic acid (DNA) studied by absorption spectroscopy and cyclic voltammetry. Binding constants and binding free energies for the FhD-DNA complex were measured using these two methods as 5100 M−1, 6109 M−1 and −21.2 kJ/mol, −21.6 kJ/mol, respectively. DFT calculations were also performed and revealed important physical characteristics of the FhD compound. Subsequently, the system was explored by computational molecular docking, confirming a non-covalent mode of binding via minor groove with a binding energy of −25.5 kJ/mol. Furthermore, molecular dynamics of the docked complex of FhD with DNA were carried out for 100 ns followed by MM-GBSA to have a deep understanding of the complex's dynamic behavior in physiological systems, and to determine the Gibbs free energy which was −14.31 Kcal/mol over a 100 ns window. The results show important antitumor potential of FhD due to its spontaneous non-covalent interaction with DNA and the efficient binding stability of the FhD-DNA complex in a physiological system. [ABSTRACT FROM AUTHOR]

The fascinating electrochemical properties of the redox-active compound ferrocene have inspired researchers across the globe to develop ferrocene-based electrocatalysts for a wide variety of applications. Advantages including excellent chemical and thermal stability, solubility in organic solvents, a pair of stable redox states, rapid electron transfer, and nontoxic nature improve its utility in various electrochemical applications. The use of ferrocene-based electrocatalysts enables control over the intrinsic properties and electroactive sites at the surface of the electrode to achieve specific electrochemical activities. Ferrocene and its derivatives can function as a potential redox medium that promotes electron transfer rates, thereby enhancing the reaction kinetics and electrochemical responses of the device. The outstanding electrocatalytic activity of ferrocene-based compounds at lower operating potentials enhances the specificity and sensitivity of reactions and also amplifies the response signals. Owing to their versatile redox chemistry and catalytic activities, ferrocene-based electrocatalysts are widely employed in various energy-related systems, molecular machines, and agricultural, biological, medicinal, and sensing applications. This review highlights the importance of ferrocene-based electrocatalysts, with emphasis on their properties, synthesis strategies for obtaining different ferrocene-based compounds, and their electrochemical applications. [ABSTRACT FROM AUTHOR]

N-ferrocenylmethylaniline (FA) and its N-acetylated derivative (NFA) have been synthesized and fully characterized by various physicochemical techniques such as 1H and 13C NMR spectroscopy, their interactions with chicken blood DNA (CB-DNA) were studied by cyclic voltammetry (CV) and molecular docking (MD). The obtained results suggested that both FA and NFA bind strongly via electrostatic interactions to the minor groove of double helix DNA, these electrostatic interactions were evidenced by the findings like a negative formal potential shift in CV and ionic strength effect. The results further show that the obtained binding constants and free binding energies by MD analysis are matched roughly to those obtained from CV. Furthermore, the binding site size was evaluated from voltametric data.

Two new ferrocene based molecules S,S′‐bis(4‐aminophenyl)ferrocene‐1,1'‐bis(carbothioate) (I) and S,S′‐bis(3‐aminophenyl)ferrocene‐1,1'‐bis(carbothioate) (II) have been synthesized via a thioester linkage. The prepared compounds have been successfully applied as ligands for the CuI catalyzed Sonogashira coupling reaction. The ligands are highly effective for the Csp2−Csp coupling between alkyne and iodobenzene and bromobenzene. Corresponding 1,2‐disubstituted alkynes could be synthesized from both aryl and alkyl alkynes in high yield by using catalytic amount of CuI in presence of bis(3‐aminophenyl)ferrocene derivative in dioxane at 50 °C. [ABSTRACT FROM AUTHOR]

Herein, a new semi‐organic aqueous flow battery based on a hydroxylated tetracationic viologen, 1,1′‐bis(3‐((2‐hydroxyethyl)dimethylammonio)propyl)‐[4,4′‐bipyridine]‐1,1′‐diium tetrachloride ([(DMAE‐Pr)2‐Vi]Cl4), and the ferrocene derivative, (ferrocenylmethyl)trimethylammonium chloride (FcNCl), is demonstrated. Efficiency, accessible capacity, and capacity retention of the battery are investigated at two concentrations of the active redox species: 0.1 and 0.5 mol dm−3 in 1 mol dm−3 KCl near‐neutral electrolytes. The implementation of the ferrocene‐derivative posolyte decreases the capacity fade rate by a factor of ≈4 with respect to previous work using 4‐hydroxy‐2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPOL) as posolyte. Capacity loss is driven by crossover of the positive redox couple into the negolyte, in particular at high concentrations, indicating the need for more selective membranes and less permeable ferrocene derivatives. Discussions are supported by conductivity measurements, cell resistance, and postmortem analysis of the electrolytes using cyclic voltammetry and nuclear magnetic resonance (NMR) spectroscopy. The characterization of [(DMAE‐Pr)2‐Vi]Cl4 is expanded as a high‐energy negolyte and future scaleup requirements for aqueous organic flow batteries are informed. [ABSTRACT FROM AUTHOR]

This paper illustrates how the size and type of substituent R in the phosphinate group of ferrocenyl bisphosphinic acids can affect conformational possibilities and coordination packing. It also demonstrates that H-phosphinate plays a key role in variational mobility, while Me- or Ph- substituents of the phosphinate group can only lead to 0D complexes or 1D coordination polymer. Overall, this paper provides valuable insights into the design and construction of coordination polymers based on ferrocene-contained linkers. It sheds light on how different reaction conditions and substituents can affect conformational possibilities and coordination packing, which could have significant implications for developing new polymers with unique properties. [ABSTRACT FROM AUTHOR]

The redox potential (ERedox) of a ferrocene (Fc) derivative differs, depending on its functional group. In this study, the various Fc derivatives are considered as mediators of anodic catalysts to promote glucose oxidation reaction (GOR) in glucose/oxygen enzymatic biofuel cells (EBFCs). Initially, their lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energies are calculated using density functional theory to predict their ERedox pattern. According to the calculations, the LUMO and HOMO energies of Fc derivatives combined with electron-donating groups (EDGs) are higher than those of Fc derivatives combined with electron-withdrawing groups (EWGs), including the results that Fc(NH2) has the highest molecular orbital (MO), while Fc(CHO) has the lowest. To verify the prediction for ERedox pattern, electrochemical evaluations are conducted. When glucose is provided, the onset potential (EOnset) of GOR is measured, while the ERedox of Fc derivatives and EOnset of GOR are linearly proportional to each other ( R 2 = 0.98) and DFT calculations. As the energies increase, the above two potentials are shifted more negatively. More specifically, the ERedox of Fc(NH2) and EOnset of GOR show the most negative values at (−0.112 and −0.17) V, respectively, while the ERedox of Fc(CHO) and EOnset of GOR show the most positive values at (0.496 and 0.40) V, respectively. Then, when this correlation is adopted for EBFCs, EBFCs using Fc(NH2) combined with EDG show 3.7 times higher maximum power density than those using Fc(COOH), as representatives combined with EWG. Based on that, it is well established how DFT and electrochemical evaluations should be used to design anodic catalysts including Fc derivatives as mediators for GOR. [ABSTRACT FROM AUTHOR]

Ferrocenyl-based compounds have many applications in diverse scientific disciplines, including in polymer chemistry as redox dynamic polymers and dendrimers, in materials science as bioreceptors, and in pharmacology, biochemistry, electrochemistry, and nonlinear optics. Considering the horizon of ferrocene chemistry, we attempted to condense the neoteric advancements in the synthesis and applications of ferrocene derivatives reported in the literature from 2016 to date. This paper presents data on the progression of the synthesis of diverse classes of organic compounds having ferrocene scaffolds and recent developments in applications of ferrocene-based organometallic compounds, with a special focus on their biological, medicinal, bio-sensing, chemosensing, asymmetric catalysis, material, and industrial applications. [ABSTRACT FROM AUTHOR]

Mono-, bi- and trinuclear carbinol derivatives of ferrocene C5H5FeC5H4-C(CH3)2OH (I), [C5H5FeC5H4]2C(CH3)OH (II), [C5H5FeC5H4]3C-OH (III) were synthesized. the thermal stability and thermodynamics of the pyrolysis of these compounds have been studied. The composition and structure of the synthesized compounds were established by elemental analysis (AAS, C, H analysis), 1H NMR, IR, and UV/visible spectroscopy. In the IR spectra of these compounds there are absorption bands with ν(OH) =2910-3040 cm-1 and ν(OH) = 3080-3190 cm-1, and in the 1H NMR spectra there are absorption bands with chemical shift values δ(OH) = 4.29-4.18 ppm for OH groups that differ in position and are due to the formation of intra- and intermolecular associates with the participation of OH groups. The electronic absorption spectra indicate the presence of characteristic absorption bands in compounds I-III at λmax = 270 (I), 278 (II), and 285 nm (III). It is shown that when samples are heated from room temperature to 700 °C in an inert gas flow, the residual mass of compounds I-III is 2.05, 20.24, and 66.96% of the initial mass, respectively, and these compounds decompose to form nanosized iron particles. /iron oxide and carbon. The values of the melting temperature and saturation magnetization of nanosized iron particles formed during the pyrolysis of ferrocene and its derivatives I-III are calculated. [ABSTRACT FROM AUTHOR]

The synthesis of novel 1,1′‐disubstituted ferrocene conjugates appended with N‐1 and O‐4 alkylated quinolone and quinoline was reported. The target compounds were synthesized employing a liquid‐assisted grinding (LAG) mechanochemical method in copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) to obtain ferrocene−quinoline/quinolone hybrids (5a–5d, 6a–6d, 7a, 7b, 8a, and 8b) in higher yields and shorter reaction time compared to a conventional method, thus proving superiority of mechanochemistry versus conventional synthesis. Bis‐quinoline and bis‐quinolone ferrocene derivatives were evaluated for their antiproliferative effects on five selected tumor and two non‐tumor cell lines. Bis‐6‐methylquinolone–ferrocene conjugate 8b showed the best antiproliferative effect on T‐cell lymphoma (HuT78) cells (IC50 = 14.8 μM) and no cytotoxicity on both non‐tumor MDCK1 and BJ cells. Results obtained after mitochondrial membrane potential (∆Ψm) measurement using flow cytometry showed that compound 8b caused accumulation of HuT78 cells in subG0/G1 phase, disturbance of mitochondrial membrane potential, and apoptosis. The structure of the quinolone and ferrocene hybrid 8b can be further optimized to obtain candidates with better inhibitory effects on HuT78 cells. [ABSTRACT FROM AUTHOR]

Ferrocene derivatives are amongst the most promising electroactive organic electrolytes. The bottleneck problems of their application in aqueous redox flow batteries are their poor solubility and lower potential as well as the complexity of the modification methods to solve these problems. In this study, a benzenesulfonic acid group is easily introduced into the ferrocene structure by a mature diazotization reaction, and the synthesized sodium m-phenylferrocene sulfonate BASFc is used as the novel cathodic electroactive electrolyte for AORFB. The hydrophilicity and the electron-absorbing effect of the introduced benzenesulfonic group can effectively improve the water solubility and redox potential of ferrocene. Moreover, the introduction of phenyl extends the conjugated structure of ferrocene and increases its structural dimension, which may be conducive to reducing its membrane permeability and improving the structural stability to some extent. The physical structure and the electrochemical properties of BASFc are studied systematically; the feasibility of its application as a cathodic electrolyte in AORFBs is verified by assembling the half-cell and full-cell. The results verify the good electrochemical reaction kinetics of BASFc in acid electrolyte and the corresponding AORFB shows satisfactory efficiency and stability. [ABSTRACT FROM AUTHOR]

The development of new and efficient chiral extractants has always been the research hotspot and difficulty in the field of chiral extraction. Josiphos, a famous ferrocene derivative catalyst, is employed as a chiral extractant in enantioseparation of amino acid and mandelic acid enantiomers. The influences of metal ions, organic solvents, pH of the aqueous solution, extractant concentrations, and extraction temperature on enantioselectivities are systematically studied. The result reveals that Josiphos‐Pd has good capabilities to enantioseparate 4‐nitro‐phenylalanine (Nphe), 3‐chloro‐phenylglycine (Cpheg), and mandelic acid (MA) with separation factors (α) of 3.30, 2.65, and 2.18, respectively. The pH of the aqueous phase and Josiphos‐Pd concentration affect the extraction significantly, whereas extraction temperature shows little influence. After optimizing by response surface method, the mathematical models for extractions are established. And the highest experimental performance factors (pf) for Nphe, Cpheg, and MA are 0.1843, 0.1335, and 0.08884, respectively. [ABSTRACT FROM AUTHOR]

The functionalization of (R,R)-S,S′-di-tert-butylferrocene-1,1′-disulfoxide by deprotolithiation-electrophilic trapping sequences was studied towards polysubstituted, enantiopure derivatives for which the properties were determined. While the 2,2′-disubstituted ferrocene derivatives were obtained as expected, subsequent functionalization of the 2,2′-di(phenylthio) and 2,2′-bis(trimethylsilyl) derivatives occurred primarily at the 4- or 4,4′-positions. This unusual regioselectivity was discussed in detail in light of pKa values and structural data. The less sterically hindered 2,2′-difluorinated derivative yielded the expected 1,1′,2,2′,3,3′-hexasubstituted ferrocenes by the deprotometallation-trapping sequence. Further functionalization proved possible, leading to early examples of 1,1′,2,2′,3,3′,4,4′-octa, nona and even decasubstituted ferrocenes. Some of the newly prepared ferrocene-1,1′-disulfoxides were tested as ligands for enantioselective catalysis and their electrochemical properties were investigated. [ABSTRACT FROM AUTHOR]

Ferrocene and its derivatives are very useful in the fields of chemistry, biomedicine and materials. Herein, a ferrocene derivative was synthesized in one step from benzotriazol-1-yl-oxytripyrrolidino-phosphonium hexafluorophosphate and ferrocenecarboxylic acid. Its accurate structure was determined by 1H and 13C NMR and further confirmed by X-ray diffraction analysis of the corresponding single crystal. [ABSTRACT FROM AUTHOR]

We have investigated the electronic and transport properties of a series of 2D Fc(X)n–MoS2 (Fc=Fe(Cp)2; X=SiH2, CH2, CH=CH, or C≡C; n = 1 or 2) systems by using ferrocene derivatives Fc(X)n to be grafted onto a MoS2 surface. Calculations have been carried out by density functional theory (DFT) and nonequilibrium Green's function (NEGF) methods. All these Fc(X)n–MoS2 give type-II heterostructures, and the grafted Fc(X)n behaves as a quantum dot-like group. No matter which Fc(X)n group is introduced, the conductivity is improved. The current magnitudes at a certain bias voltage follow the sequence of Fc(C≡C)-MoS2 ≈ Fc(CH=CH)-MoS2 > Fc(SiH2)2-MoS2 ≈ Fc(SiH2)-MoS2 > Fc(CH2)2-MoS2 ≈ Fc(CH2)-MoS2, corresponding well to the abilities of supplying electrons from the (X)n group to MoS2. The armchair direction exhibits a larger current by about 4 times compared to the zigzag direction. A distinct NDR behavior is found for the Fc(C≡C)-MoS2, meaning that the transport channel can be electrically switched from the off state to the on state, and again turned to the off state. [ABSTRACT FROM AUTHOR]

• Ferrocenyl derivatives are attractive and interesting scaffolds for developing anticancer drugs for various cancer cell lines. • Ferrocene-phenol derivative known as ferrocifen is in the pre-clinical trial against breast cancer. • The structure-activity relationship with their IC 50 value is disclosed. Organometallic compounds have gained popularity as potent anti-cancer therapeutic prospects in recent years. The constant threat of drug-resistant cancer and the limited specificity of anti-cancer drugs, which necessitate the urgent development of novel anti-cancer agents, are the principal obstacles to controlling and eradicating cancer. Primarily ferrocene derivatives, considered a prime example of an organometallic compound, have remarkable structural and mechanistic diversity, inherent stability against air and temperature, low toxicity, inexpensive, reversible redox properties, ligand exchange, and catalytic properties, making them promising potential drugs for cancer prevention and treatment. Significant effort has been made to isolate and synthesize ferrocene derivatives with improved anti-cancer activity due to the prospective utilization of ferrocene in the treatment of cancer chemotherapy. In order to assist both academics and researchers interested in the development of novel and effective pharmaceuticals to address cancer therapy in this discipline, we have focused our efforts in this review article on providing a broad overview of the most recent research publications of ferrocenyl moieties with potential applications in cancer treatment (2015-present). [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] The efficient elimination of bacteria within the dentinal tubules has been hindered by the poor deposition and short residence of disinfecting agents. Meanwhile, the current irrigant (e.g., NaClO, 5.25 %) shows severe adverse effects on the surrounding soft tissues because of its inherent high irritancy. To address this issue, this work reports an in situ generated sonosensitizer to handle the biofilm in dentinal tubules with minimal adverse effects. The production of nanoscale sonosensitizer involves the concurrent delivery of H 2 O 2 (0.01 %), ferrocene derivative (Fc), and indocyanine green (ICG). With ultrasound treatment, the reaction between H 2 O 2 and Fc liberated Fe3+ that was further complexed with ICG to generate the nanoscale sonosensitizer in situ , followed by singlet oxygen production for potent disinfecting action. Because the above cascade reactions occur within the confined dentinal tubules, the generated ICG-Fe3+ nanosensitizer would show prolonged retention therein. The anti-bacterial potency of nanosensitizer was demonstrated in petrodish and ex vivo biofilm models. Meanwhile, the transmission electron microscope imaging of biofilm and cytotoxicity assay in L929 fibroblast cells proved the superiority of nanosensitizer against NaClO regarding adverse effects. The current work opens new avenues of biofilm elimination in dentinal tubules, showing a high translation potential. [ABSTRACT FROM AUTHOR]

The (C60CN)− formed by the reaction of CN− with fullerene shows high electron rich character, very similar to C60˙−, and it behaves as a large anion. Similar to Cp−, the bulky anion, (C60CN)−, acts as a strong η5 ligand towards transition metal centers. Previous studies on η5 coordination of fullerene cage are reported for pseudo fullerenes whereas the present study deals with sandwich complexes of (C60CN)− with Fe(II), Ru(II), Cr(II), Mo(II), and Ni(II) and multi‐decker sandwich complexes of CN–fullerides with Fe(II). The structural parameters of these complexes and the corresponding Cp− complexes showed very close resemblance. Analysis of the metal‐to‐carbon bonding molecular orbitals showed that sandwich complex [Fe(η5‐(C60CN)−)2] exhibit bonding features very similar to that of ferrocene. Also, a 6‐fold decrease in the band gap energy is observed for [Fe(η5‐(C60CN)−)2] compared to ferrocene. The energy of dissociation (ΔE) of the ligand (C60CN)− from [Fe(η5‐(C60CN)−)2] is slightly lower than the ΔE of a Cp* ligand from a ferrocene derivative wherein each cyclopentadienyl unit is substituted with four tertiary butyl groups. The (C60CN)− ligand behaved as one of the bulkiest ligands in the chemistry of sandwich complexes. Further, the coordinating ability of the dianion, (C60(CN)2)2− is evaluated which showed strong coordination ability simultaneously with two metal centers leading to the formation of multi‐decker sandwich and pearl‐necklace type polymeric structures. [ABSTRACT FROM AUTHOR]

Carbon dioxide (CO2) is considered as a green and renewable C1 feedstock. However, due to its thermodynamic and kinetic stability, transition metal-catalyzed carboxylation of unactivated C–H bonds with CO2 still remains challenging. Herein, a protocol for Rh(II)-catalyzed and CO2-involved carboxylation of inert sp2 C–H bonds from the cyclopentadienyl (Cp) ring of ferrocene derivatives was reported, which produces a series of ferrocene-embedded lactones that are important molecular skeletons widely used in pharmaceuticals or ligands. Moreover, moderate enantioselectivity was achieved with a chiral NHC ligand, which can be regarded as the first example for asymmetric C–H carboxylation with CO2. Preliminary mechanistic experiments supported bivalent rhodium as the real active catalyst, and a reasonable catalytic cycle was proposed accordingly. [ABSTRACT FROM AUTHOR]

Carbon dioxide (CO2) is considered as a green and renewable C1 feedstock. However, due to its thermodynamic and kinetic stability, transition metal-catalyzed carboxylation of unactivated C–H bonds with CO2 still remains challenging. Herein, a protocol for Rh(II)-catalyzed and CO2-involved carboxylation of inert sp2 C–H bonds from the cyclopentadienyl (Cp) ring of ferrocene derivatives was reported, which produces a series of ferrocene-embedded lactones that are important molecular skeletons widely used in pharmaceuticals or ligands. Moreover, moderate enantioselectivity was achieved with a chiral NHC ligand, which can be regarded as the first example for asymmetric C–H carboxylation with CO2. Preliminary mechanistic experiments supported bivalent rhodium as the real active catalyst, and a reasonable catalytic cycle was proposed accordingly. [ABSTRACT FROM AUTHOR]

Copyright of Chinese Journal of Explosives & Propellants is the property of Chinese Journal of Explosives & Propellants Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Cholesteric liquid crystals (CLC) were widely used in optical devices as one-dimensional photonic crystals. However, their reflective bands cannot be adjusted, which limits their wide application in many fields. In this paper, a series of ionic chiral ferrocene derivatives (CD-Fc+) as dopants were designed and prepared, and their doping into negative liquid crystal matrix was investigated to develop cholesteric response liquid crystal composites with electrically tunable reflective bands. The effects of electric field frequency, voltage, retention time of voltage and molecular structure on the broadening of reflection bandwidth were investigated in detail. [ABSTRACT FROM AUTHOR]

A coordination polymer has been synthesized using ferrocene-based ligand-bearing phosphinic groups of 1,1′-ferrocene-diyl-bis(H-phosphinic acid)), and samarium (III). The coordination polymer's structure was studied by both single-crystal and powder XRD, TG, IR, and Raman analyses. For the first time, the Mössbauer effect studies were performed on ferrocenyl phosphinate and the polymer based on it. Additionally, the obtained polymer was studied by the method of cyclic and differential pulse voltammetry. It is shown that it has the most positive potential known among ferrocenyl phosphinate-based coordination polymers and metal–organic frameworks. Using the values of the oxidation potential, the polymer was oxidized and the ESR method verified the oxidized Fe(III) form in the solid state. Additionally, the effect of the size of the phosphorus atom substituent of the phosphinate group on the dimension of the resulting coordination compounds is shown. [ABSTRACT FROM AUTHOR]

Pentacoordinate carbon atoms are theoretically predicted here in a ferrocene dication derivative in the eclipsed-(1; C 2 v ), gauche-(2; C 2 ) and staggered-[Fe(Si 2 - η 5 -C 5 H 2 ) 2 ] 2 + (3; C 2 h ) forms for the first time. Energetically, the relative energy gaps for 2 and 3 range from −3.06 to 16.74 and −2.78 to 40.34 kJ mol − 1 , respectively, when compared to the singlet electronic state of 1 at different levels. The planar tetracoordinate carbon (ptC) atom in the ligand Si 2 C 5 H 2 becomes a pentacoordinate carbon upon complexation. The ligand with a ptC atom was predicted to be both a thermodynamically and kinetically stable molecule by some of us in our earlier theoretical works. Natural bond orbital and adaptive natural density partitioning analyses confirm the pentacoordinate nature of carbon in these three complexes (1–3). Although they are hypothetical at the moment, they support the idea of "hypercoordinate metallocenes" within organometallic chemistry. Moreover, ab initio molecular dynamics simulations carried out at 298 K temperature for 2000 fs suggest that these molecules are kinetically stable. [ABSTRACT FROM AUTHOR]

[Display omitted] Ferrocene and its derivatives have great potential for biomedical applications, but few related studies have been reported. In this study, copper ions and ferrocene derivatives were used for the first time to construct the ferrocene-based nanoparticles (Cu-Fc) with a hydrated particle size of approximately 220 nm. Their good photothermal conversion properties were verified in vitro and in vivo for the first time, indicating that they could be used as a novel photothermal agent for tumor treatment. In addition, the nanoparticles exhibited efficient Fenton effect under weakly acidic conditions, indicating that they can generate hydroxyl radicals (OH) to kill tumors in the weakly acidic environment of the tumor-specific microenvironment. More importantly, the nanoparticles can deplete glutathione (GSH), thus further enhancing Fenton effect-mediated chemodynamic therapy (CDT). Multifunctional ferrocene-based nanoparticles (DOX@Cu-Fc) were obtained after loading the chemotherapeutic drug doxorubicin hydrochloride (DOX). The results of in vitro and in vivo experiments showed that DOX@Cu-Fc could enhance tumor treatment by the combination of chemo/CDT/photothermal therapy (PTT). [ABSTRACT FROM AUTHOR]

During the past decades, in synthetic organic chemistry, directing‐group‐assisted C−H functionalization is found to be a key tool for the expedient and site‐selective construction of C−C and hybrid bonds. Among C−H functionalization of ferrocene derivatives, the directed group strategy is undoubtedly the most commonly used method. Compared to the other directing groups, ferrocene amides can be synthesized easily and are now recognized as one of the most efficient tools for the selective functionalization of certain positions because its metal centre permits fine, tuneable and reversible coordination. The family of amide directing groups mainly comprises monodentate and bidentate directing groups, which are categorized on the basis of coordination sites. In this review, various C−H bond functionalization reactions of ferrocene using amide directing groups are broadly discussed. [ABSTRACT FROM AUTHOR]