Ferrocenedicarboxylic Acid Research Articles

Two birds with one stone: A ferrocene-based zirconium(IV)-organic framework nanosheet denoting intrinsic high proton conductivity and acting as a fine dopant to chitosan-based composite membranes

Recently, it was demonstrated that employing metal-organic frameworks (MOFs) with prominent proton conductivity (σ) as fillers with organic substrates such as chitosan (CS) or Nafion is an effective approach for preparing composite membranes (CMs) with outstanding functionalities. Inspired by this, one extremely stable Zr(IV)-MOF (namely Zr-FDC) with a nanosheet structure produced by 1,1′-ferrocene dicarboxylic acid (H2FDA) was successfully manufactured in this research and subsequently used as a filler to synthesize a series of CS-based CMs via casting method. The alternating current (AC) impedance determinations manifested that both Zr-FDC and the related CS-based CMs (CS/MOF-x; x = 2, 4, 6, 8 being the mass percentage of Zr-MOF in the CM) showed ultrahigh σ values, indicating the structural advantages of the Zr-MOF. Further research verified that when the MOF doping quantity is 4 %, the CM's (CS/MOF-4) σ is the greatest, being 2.22 × 10−2 S/cm, which is boosted by nearly tenfold at 100 °C and 98 % relative humidity (RH) compared to the original MOF (3.2 × 10−3 S/cm). Furthermore, the CM exhibits superior thermal stability and tensile resistance. Finally, considering the structural features of the MOF and CS, activation energy data, and other determinations, we thoroughly theorized the proton conduction process within the MOF framework and CMs, referencing the subsequent proton exchange membrane design.

A Novel Ferrocene-Linked Thionine as a Dual Redox Mediator for the Electrochemical Detection of Dopamine and Hydrogen Peroxide.

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.

Ferrocene-based 2D metal–organic framework nanosheet for highly efficient photocatalytic seawater uranium recovery

Sustainable uranium supply is critical for the long-term development of nuclear energy. The photocatalytic reduction of soluble hexavalent uranium to insoluble tetravalent uranium using photocatalysts has been recognized as a highly promising method for uranium recovery. However, existing photocatalysts face limitations such as restricted visible-light absorption and poor charge transfer capability, which hinder their photocatalytic uranium recovery performance. In this work, 1,1′-ferrocene dicarboxylic acid (FcDA) was introduced to synthesize the photocatalyst Zr-Fc-MOF3. The incorporation of FcDA broadened the visible light absorption range and reduced the band gap of Zr-Fc-MOF3, thereby enhancing electron-hole pair separation and carrier transport efficiencies. Moreover, the two-dimensional (2D) nanosheet structure of Zr-Fc-MOF3 provided a large surface area, allowing full exposure of active sites. Additionally, Fe(II) in FcDA generated photoelectrons upon light excitation to facilitate uranium reduction, and the recyclable redox behavior of Fe(II) conferred high reusability of the photocatalyst. Consequently, Zr-Fc-MOF3 demonstrated a high photocatalytic uranium recovery capacity of 8.29 mg g−1 over 10 days in natural seawater (NSW), with a uranium recovery rate of 0.829 mg g−1 d−1, surpassing most other photocatalysts applied in NSW. These findings suggest that designing 2D nanosheet materials with ligands capable of efficient photoelectron generation is a promising approach for developing high-performance uranium recovery photocatalysts.

Nickel-Based Metal-Organic Framework Materials with Mixed Ferrocene-Based Ligands As Anodic Catalysts for Water Electrolysis and Urea Electrolysis

Water electrolysis is a highly promising technology for hydrogen production, generating green hydrogen with no greenhouse gas emissions. The water electrolysis reaction involves two half-reactions: hydrogen evolution and oxygen evolution. While oxygen evolution in water electrolysis involves a four-electron transfer requiring higher overpotential and thus leading to energy consumption. Urea electrolysis offers lower theoretical energy consumption than water electrolysis, making them a key technology in future electrolytic hydrogen production processes. Conventional anodic catalysts, such as Ir and Ru, exhibit good performance in oxygen evolution, but being precious metals, they face limitations due to high cost and limited abundance. Its is crucial to find an active, durable and cost-effective anode catalyst for realistic application.Metal-organic framework (MOF) materials, due to their high porosity, large surface area, and unique structural features, have emerged as promising materials for water electrolysis. However, their relatively poor stability is a drawback that needs to be overcome. In herein, we design the mixed ligand strategy for synthesizing the MOF materials. Ferrocene-based ligands, ferrocenedicarboxylic acid (Fd), combing with terephthalic acid (H2BDC) as the mixed ligands for this study. The MOF catalysts, namely Ni-BDC and Ni-BDC-Fd, was synthesized using a simple one-step hydrothermal method with ferrocenedicarboxylic acid and terephthalic acid.Raman spectra revealed the presence of Fe-O, originating from the iron in Fd, demonstrating a structural transformation during the hydrothermal process. XRD analysis also confirmed the existence of FeO. The SEM images showed nanosheets and nanoneedles morphologies for Ni-BDC, while a dense nanofiber structure for Ni-BDC-Fd demonstrating the effect of 2nd ligand on the MOF structure.Electrochemical tests were conducted in 1 M KOH electrolyte and 1 M KOH + 0.5 M urea electrolyte, including oxygen evolution reaction (OER), urea oxidation reaction (UOR). The overall reaction comprising the same catalysts for the anode and the cathode side is performed to examine the real electrolysis performance.Results showed that the addition of Fd enhanced OER and UOR activity in alkaline and urea electrolytes. Ni-BDC-Fd achieved 1.483 V vs. RHE and 1.386 V vs. RHE at 65 mA/cm-2 driving potential for OER and UOR, respectively, requiring a smaller potential than Ni-BDC to achieve the same current density. To verify that the performance improvement was not solely due to iron, NiFe-BDC was synthesized by adding iron nitrate, showing inferior UOR performance compared to Ni-BDC-Fd but superior OER performance to NiFe-BDC. This indicated that the performance improvement resulted from structural changes rather than just the presence of iron atoms. Ni-BDC-Fd exhibited the lowest Tafel slope in OER, indicating a faster reaction rate due to the increased active surface area during OER. After continuous catalysis for 80 hours in the alkaline water electrolysis cell and urea electrolysis cell, a significant improvement in the loss of potential was observed.These results suggest that the addition of ferrocene dicarboxylic acid altered the structure of Ni-BDC, maintaining an appropriate interlayer distance. This not only enhanced its catalytic performance but also improved its catalytic stability, demonstrating a promising strategy for preparing metal-organic framework materials for electrocatalysis applications. Figure 1

Structural Reconstruction of a Cobalt- and Ferrocene-Based Metal-Organic Framework during the Electrochemical Oxygen Evolution Reaction.

Metal-organic frameworks (MOFs) are increasingly being investigated as electrocatalysts for the oxygen evolution reaction (OER) due to their unique modular structures that present a hybrid between molecular and heterogeneous catalysts, featuring well-defined active sites. However, many fundamental questions remain open regarding the electrochemical stability of MOFs, structural reconstruction of coordination sites, and the role of in situ-formed species. Here, we report the structural transformation of a surface-grown MOF containing cobalt nodes and 1,1'-ferrocenedicarboxylic acid linkers (denoted as CoFc-MOF) during the OER in alkaline electrolyte. Ex situ and in situ investigations of CoFc-MOF film suggest that the MOF acts as a precatalyst and undergoes a two-step restructuring process under operating conditions to generate a metal oxyhydroxide phase. The MOF-derived metal oxyhydroxide catalyst, supported on nickel foam electrodes, displays high activity toward the OER with an overpotential of 190 mV at a current density of 10 mA cm-2. While this study demonstrates the necessity of investigating structural evolution of MOFs during electrocatalysis, it also shows the potential of using MOFs as precursors in catalyst design.

Ferrocene-based metal-organic frameworks with dual synergistic active sites for selectively electrochemical removal of arsenic from contaminated water

The effective removal of trace levels of the highly toxic arsenite (As(Ⅲ)) from groundwater is crucial to address the threat to drinking water supply. Herein, we developed an electrochemical separation system utilizing redox-active ferrocene-based metal-organic frameworks (termed Fe-DFc) for selective removal of As(III). This system leveraged 1,1′-ferrocenedicarboxylic acid as a ligand coordinated with iron, enabling the highly selective capture and conversion of As(III) from groundwater. The Fe-DFc electrode-based electrochemical system not only effectively removed As(III) even in the presence of a 1250-fold excess of competing electrolytes, but also converted about 96 % of the adsorbed As(III) into the less toxic As(V), surpassing the results of those documented in the current literature. X-ray absorption fine structure analysis and density functional theory calculations demonstrated that the high selectivity of Fe-O6 moiety and the exceptional redox activity of Fc synergistically contributed to the efficient removal of As(III). Moreover, the electrochemical separation system enabled the remediation of arsenic-contaminated groundwater at a low energy cost of 0.033 kWh m−3 during long-term operation, highlighting the application potential of the electrochemical technology for arsenic removal from contaminated water.

Enhanced catalytic activity of Fe3O4-carbon dots complex in the Fenton reaction for enhanced immunotherapeutic and oxygenation effects

Tumor metastasis and recurrence are closely related to immune escape and hypoxia. Chemodynamic therapy (CDT), photodynamic therapy (PDT), and photothermal therapy (PTT) can induce immunogenic cell death (ICD), and their combination with immune checkpoint agents is a promising therapeutic strategy. Iron based nanomaterials have received more and more attention, but their low Fenton reaction efficiency has hindered their clinical application. In this study, Fe3O4-carbon dots complex (Fe3O4-CDs) was synthesized, which was modified with ferrocenedicarboxylic acid by amide bond, and crosslinked into Fe3O4-CDs@Fc nano complex. The CDs catalyzed the Fenton reaction activity of Fe3O4 by helping to improve the electron transfer efficiency, extended the reaction pH condition to 7.4. The Fe3O4-CDs@Fc exhibit exceptional optical activity, achieving a thermal conversion efficiency of 56.43 % under 808 nm light and a photosensitive single-line state oxygen quantum yield of 33 % under 660 nm light. Fe3O4-CDs@Fc improved intracellular oxygen level and inhibited hypoxia-inducing factor (HIF-1α) by in-situ oxygen production based on Fenton reaction. The multimodal combination of Fe3O4-CDs@Fc (CDT/PDT/PTT) strongly induced immune cell death (ICD). The expression of immune-related protein and HIF-1α was investigated by immunofluorescence method. In vivo, Fe3O4-CDs@Fc combined with immune checkpoint blocker (antibody PD-L1, αPD-L1) effectively ablated primary tumors and inhibited distal tumor growth. Fe3O4-CDs@Fc is a promising immune-antitumor drug.

Tailored Porous Ferrocene-Based Metal-Organic Frameworks as High-Performance Proton Conductors.

Although crystalline metal-organic frameworks (MOFs) have gained a great deal of interest in the field of proton conduction in recent years, the low stability and poor proton conductivity (σ) of some MOFs have hindered their future applications. As a result, resolving the issues listed above must be prioritized. Due to their exceptional structural stability, MOFs with ferrocene groups that exhibit particular physical and chemical properties have drawn a lot of attention. This study describes the effective preparation of a set of three-dimensional ferrocene-based MOFs, MIL-53-FcDC-Al/Ga and CAU-43, containing both main group metals and 1,1'-ferrocene dicarboxylic acid (H2FcDC). Multiple measurements, including powder X-ray diffraction (PXRD), infrared (IR), and scanning electron microscopy (SEM), confirmed that the addition of ferrocene groups enhanced the thermal, water, and acid-base stabilities of the three MOFs. Consequently, their proton-conductive behaviors were meticulously measured utilizing the AC impedance approach, and their best proton conductivities are 5.20 × 10-3, 2.31 × 10-3, and 1.72 × 10-4 S/cm at 100 °C/98% relative humidity (RH), respectively. Excitingly, MIL-53-FcDC-Al/Ga demonstrated an extraordinarily ultrahigh σ of above 10-4 S·cm-1 under 30 °C/98% RH. Using data from structural analysis, PXRD, SEM, thermogravimetry (TG), and activation energy, their proton transport mechanisms were thoroughly examined. The fact that these MOFs are notably easy to assemble, inexpensive, toxin-free, and stable will increase the range of practical uses for them.

Ru nanoparticles decorating ferrocene-based metal-organic framework for efficient and stable water-splitting electrocatalyst

The development of stable and efficient electrocatalysts based on metal-organic frameworks represents a main challenge for the overall water splitting process. Here, the ferrocene-based nickel metal-organic framework (NiFc-MOF) on nickel foam (NF) was synthesized using nickel chloride and 1, 1′-ferrocenedicarboxylic acid (FcDA) via a simple solvothermal method, and Ru nanoparticles (NPs) were reduced by FcDA and in situ grown on the surface of NiFc-MOF nanosheets. The as-prepared cactus-like Ru0.3@NiFc-MOF exhibits high electrocatalytic activity for hydrogen evolution reaction (HER) with a low overpotential of 25 mV@10 mA cm−2 and a Tafel slope of 45.05 mV dec−1. To reach a current density of 10 mA cm−2 for the oxygen evolution reaction (OER), a low overpotential of 210 mV was required. The assembled water electrolysis cell using Ru0.3@NiFc-MOF as bifunctional electrocatalysts only requires a voltage of 1.47 V to achieve a current density of 10 mA cm−2, indicating excellent electrolytic water splitting performance. In addition, the electrocatalytic activity of Ru0.3@NiFc-MOF's can keep the stability for 120 h Ru0.3@NiFc-MOF exhibits exceptional electrocatalytic performance, which can be attributed to both the intrinsic activity of Ru sites and the multiple active sites of NiFc-MOF.

Immunoantitumor Activity and Oxygenation Effect Based on Iron-Copper-Doped Folic Acid Carbon Dots.

Cancer metastasis and recurrence are closely associated with immunosuppression and a hypoxic tumor microenvironment. Chemodynamic therapy (CDT) and photothermodynamic therapy (PTT) have been shown to induce immunogenic cell death (ICD), effectively inhibiting cancer metastasis and recurrence when combined with immune adjuvants. However, the limited efficacy of Fenton's reaction and suboptimal photothermal effect present significant challenges for successfully inducing ICD through CDT and PTT. This paper described the synthesis and immunoantitumor activity of the novel iron-copper-doped folic acid carbon dots (CFCFB). Copper-doped folic acid carbon dots (Cu-FACDs) were initially synthesized via a hydrothermal method, using folic acid and copper gluconate as precursors. Subsequently, the nanoparticles CFCFB were obtained through cross-linking and self-assembly of Cu-FACDs with ferrocene dicarboxylic acid (FeDA) and 3-bromopyruvic acid (3BP). The catalytic effect of carbon dots in CFCFB enhanced the activity of the Fenton reaction, thereby promoting CDT-induced ICD and increasing the intracellular oxygen concentration. Additionally, 3BP inhibited cellular respiration, further amplifying the oxygen concentration. The photothermal conversion efficiency of CFCFB reached 55.8%, which significantly enhanced its antitumor efficacy through photothermal therapy. Immunofluorescence assay revealed that treatment with CFCFB led to an increased expression of ICD markers, including calreticulin (CRT) and ATP, as well as extracellular release of HMGB-1, indicating the induction of ICD by CFCFB. Moreover, the observed downregulation of ARG1 expression indicates a transition in the tumor microenvironment from an immunosuppressive state to an antitumor state following treatment with CFCFB. The upregulation of IL-2 and CD8 expression facilitated the differentiation of effector T cells, resulting in an augmented population of CD8+ T cells, thereby indicating the activation of systemic immune response.

A novel composite of covalent organic framework and molecularly imprinted polymer with 1,1′-bis(allylcarbamoyl)ferrocene as cross-linker for ratiometric electrochemical detection of 5-hydroxytryptamine

A novel covalent organic framework and molecularly imprinted polymer (COF-MIP) composite, incorporating 1,1′-bis(allylcarbamoyl)ferrocene (AC-Fc) as a cross-linker, was synthesized through free radical polymerization for the ratiometric electrochemical detection of 5-hydroxytryptamine (5-HT). The AC-Fc cross-linker was synthesized using 1,1′-ferrocenedicarboxylic acid as a reactant. Subsequently, the COF-MIP was prepared using surface imprinting technique, employing AC-Fc as the cross-linker, COF as the supporter, and 5-HT as the template. The COF-MIP was employed in the development of a ratiometric electrochemical sensor for 5-HT. Upon 5-HT introduction, the peak current of 5-HT exhibited a concentration-dependent increase, while that for ferrocene (Fc) remained nearly constant. By utilizing Fc and 5-HT peak currents as reference and indicator signals, respectively, 5-HT was quantitatively determined. The ratio of I5-HT/IFc for the COF-MIP sensor was 4.69, 3.69, and 1.98 times higher than those of non-imprinted polymer (NIP), traditional MIP, and COF-NIP sensors, respectively. The ratiometric sensor with COF-MIP demonstrated a linear ratiometric signal (I5-HT/IFc) in response to 5-HT concentrations within the range of 0.2–10 µM, with a detection limit of 0.03 µM. The relative standard deviation of the non-ratiometric and ratiometric sensors was 8.7% and 2.7%, respectively. This methodology was successfully employed for the detection of 5-HT in human serum.

A novel Ce/Fe bimetallic metal-organic framework with ortho-dodecahedral multilevel structure for enhanced phosphate adsorption

The synthesis of novel Ce/Fe bimetallic metal–organic frameworks (Ce/FcDA/FA-MOFs) via an innovative hydrothermal method is reported. This method utilizes Ce as the central metal and 1,1′-ferrocene dicarboxylic acid (FcDA) and formic acid (FA) as ligands. Optimization of hydrothermal time, feed ratio, and the addition of FA yielded Ce/FcDA/FA-MOFs with ideal ortho-dodecahedral hierarchical configurations. Comprehensive characterization via FT-IR, XRD, SEM, EDS, XPS, and N2 adsorption/desorption analyses elucidated the influence of FA on morphology and chemical structure. Phosphate adsorption tests on Ce/FcDA/FA-MOFs revealed sustained strong selectivity and adsorption capacity, even in the presence of coexisting anions and variations in pH. Kinetic, thermodynamic, and isothermal simulations indicated spontaneous, efficient, and heat-absorbing phosphate adsorption properties on Ce/FcDA/FA-MOFs. Fitting parameters from the Langmuir adsorption model demonstrated a maximum adsorption capacity of up to 530.25 mg g−1, attributed to physical/chemical adsorption during the reaction. Furthermore, investigation into the adsorption mechanism of Ce/FcDA/FA-MOFs on phosphate through FT-IR, XRD, and XPS analyses of the adsorbed samples revealed a complex process involving the electrostatic mutual attraction of outer-sphere entities and ligand exchange in the inner-sphere. This study advances our understanding of Ce/FcDA/FA-MOFs as effective adsorbents for phosphate and contributes to the development of environmentally sustainable materials with potential applications in water treatment.

Metal‐Organic Frameworks: Direct Synthesis by Organic Acid‐Etching and Reconstruction Disclosure as Oxygen Evolution Electrocatalysts

AbstractMetal‐organic frameworks (MOFs) have emerged as promising oxygen evolution reaction (OER) electrocatalysts. Chemically bonded MOFs on supports are desirable yet lacking in routine synthesis, as they may allow variable structural evolution and the underlying structure‐activity relationship to be disclosed. Herein, direct MOF synthesis is achieved by an organic acid‐etching strategy (AES). Using π‐conjugated ferrocene (Fc) dicarboxylic acid as the etching agent and organic ligand, a series of MFc‐MOF (M=Ni, Co, Fe, Zn) nanosheets are synthesized on the metal supports. The crystal structure is studied using X‐ray diffraction and low‐dose transmission electron microscopy, which is quasi‐lattice‐matched with that of the metal, enabling in situ MOF growth. Operando Raman and attenuated total reflectance Fourier transform infrared spectroscopy disclose that the NiFc‐MOF features dynamic structural rebuilding during OER. The reconstructed one showing optimized electronic structures with an upshifted total d‐band center, high M−O bonding state occupancy, and localized electrons on adsorbates indicated by density functional theory calculations, exhibits outstanding OER performance with a fairly low overpotential (130 mV at 10 mA cm−2) and good stability (144 h). The newly established approach for direct MOF synthesis and structural reconstruction disclosure stimulate the development of more prudent catalysts for advancing OER.

Metal-Organic Frameworks: Direct Synthesis by Organic Acid-Etching and Reconstruction Disclosure as Oxygen Evolution Electrocatalysts.

Metal-organic frameworks (MOFs) have emerged as promising oxygen evolution reaction (OER) electrocatalysts. Chemically bonded MOFs on supports are desirable yet lacking in routine synthesis, as they may allow variable structural evolution and the underlying structure-activity relationship to be disclosed. Herein, direct MOF synthesis is achieved by an organic acid-etching strategy (AES). Using π-conjugated ferrocene (Fc) dicarboxylic acid as the etching agent and organic ligand, a series of MFc-MOF (M=Ni, Co, Fe, Zn) nanosheets are synthesized on the metal supports. The crystal structure is studied using X-ray diffraction and low-dose transmission electron microscopy, which is quasi-lattice-matched with that of the metal, enabling in situ MOF growth. Operando Raman and attenuated total reflectance Fourier transform infrared spectroscopy disclose that the NiFc-MOF features dynamic structural rebuilding during OER. The reconstructed one showing optimized electronic structures with an upshifted total d-band center, high M-O bonding state occupancy, and localized electrons on adsorbates indicated by density functional theory calculations, exhibits outstanding OER performance with a fairly low overpotential (130 mV at 10 mA cm-2 ) and good stability (144 h). The newly established approach for direct MOF synthesis and structural reconstruction disclosure stimulate the development of more prudent catalysts for advancing OER.

Особенности строения полифункциональных карбоксилатов тетраарилсурьмы

From ferrocenedicarboxylic acid, sulfosalicylic acid and pentaarylantimony Ar5Sb (Ar = Ph, p-Tol) in benzene, fully substituted organoantimony derivatives of ferrocenedicarboxylic and sulfosalicylic acids 1–3 were obtained, the structure of which after recrystallization from a benzene-octane mixture was proven by X-ray diffraction analysis. Structures 1–3 were established by X-ray diffraction. Crystals 1 [C68H64FeO4Sb2, M 1244.54; monoclinic syngony, symmetry group C21/c; cell parameters: a = 16.9983(2), b = 10.94570(10), c = 30.3224(3) Å; β = 99.8220(10); V = 5559.04(10) Å3; Z = 4; calc = 1.487 g/cm3; 2 5.28138.76 degrees; total reflections 32707; independent reflections 10281; number of specified parameters 684; Rint = 0.0496; GOOF 1.062; R1 = 0.0345, wR2 = 0.0853; residual electron density (max/min) 0.76/0.90 e/Å3], 2 [C60H48FeO4Sb2, M 1132.33; monoclinic syngony, symmetry group P21/n; cell parameters: a = 12.40720(10), b = 10.30830(10), c = 36.7290(4) Å; β = 94.1110(10) deg., V = 4685.45(8) Å3, Z = 4; calc = 1.605 g/cm3; 2 4.82138.56 degrees; total reflections 27748; independent reflections 8680; number of specified parameters 604; Rint = 0.0367; GOOF 1.033; R1 = 0.0277, wR2 = 0.0709; residual electron density (max/min) 0.86/0.81 e/Å3], 3 [C63H62O7SSb2, M 1206.78; monoclinic syngony, symmetry group P21/c; cell parameters: a = 20.9246(3), b = 13.5375(2), c = 21.4222(3) Å; β = 111.284(2) deg., V = 5654.30(16) Å3, Z = 4; calc = 1.4175 g/cm3; 2 4.54160 degrees; total reflections 48463; independent reflections 11892; number of specified parameters 699; Rint = 0.0443; GOOF 1.024; R1 = 0.0327, wR2 = 0.0907; residual electron density (max/min) 0.93/0.85 e/Å3]. The antimony atoms in molecules 1, 2 have a distorted octahedral configuration, taking into account the coordination of the carbonyl oxygen atoms to the metal atom. Structure 3 contains tetrahedral tetraaryl stibonium cations, the antimony atoms in which are coordinated with the oxygen atoms of sulfo groups (Sb∙∙∙O(5)=S 2.601 Å), and the same oxygen atom is coordinated with the ortho-hydrogen atom of one of the tolyl groups (H(46)∙∙∙O(5)=S 2.60 Å). Water molecules provide a structure to crystal 3 (H(7)∙∙∙O(4)=S 1.98 Å, H(7)∙∙∙O(5)=S 2.60 Å). (CCDC 2320709 for 1, 2320711 for 2, 2320717 for 3; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).

Fabrication of flower-like CoFe/C composites derived from ferrocene-based metal-organic frameworks: an in situ growth strategy toward high-efficiency electromagnetic wave absorption.

Magnetic/dielectric composites can achieve high-efficiency electromagnetic wave (EMW) absorption performance by integrating multiple mechanisms such as dielectric loss and magnetic loss. The bimetallic metal-organic frameworks (MOFs) assembled from ferrocene (Fc) derivative-based bridging ligands are considered ideal precursors for the preparation of magnetic/dielectric composites due to tailored alloy components with magnetic losses. Herein, a novel CoFe/C composite with nanoflower structures is successfully obtained via an in situ growth strategy to decompose an Fc-based bimetallic MOF assembled from 1,1'-ferrocene dicarboxylic acid as bridging ligands and Co2+ ions. Notably, the nanoflower structures of the obtained composites provide an effective path for the scattering and reflection of the EMW, thereby improving the impedance matching by combining dielectric and magnetic loss. The CoFe/C composite exhibits excellent EMW absorption performance and has a minimum reflection loss of -61.6 dB at 3.7 mm and an effective absorption bandwidth of 6.24 GHz at a corresponding thickness of 2.2 mm. Moreover, the obtained composite exhibits lightweight characteristics and a low radar cross-section. This work presents a novel method through Fc-based bimetallic MOF derivatives to design and develop novel magnetic/dielectric composites with efficient EMW absorption properties for comprehensive applications.

In situ growth of a redox-active metal-organic framework on electrospun carbon nanofibers as a free-standing electrode for flexible energy storage devices.

The rational construction of free-standing and flexible electrodes for application in electrochemical energy storage devices and next-generation supercapacitors is an emerging research focus. Herein, we prepared a redox-active ferrocene dicarboxylic acid (Fc)-based nickel metal-organic framework (MOF) on electrospun carbon nanofibers (NiFc-MOF@CNFs) via an in situ approach. This in situ approach avoided the aggregation of the MOF. The NiFc-MOF@CNF flexible electrode showed a high redox-active behavior owing to the presence of ferrocene and flexible carbon nanofibers, which led to unique properties, including high flexibility and lightweight. Furthermore, the prepared electrode was utilized in a supercapacitors (SC) without the use of any binder, which achieved a specific capacity of 460 C g-1 at 1 A g-1 with an excellent cyclic retention of 82.2% after 25 000 cycles and a good rate capability. A flexible asymmetric supercapacitor device was assembled, which delivered a high energy density of 56.25 W h kg-1 and a long-lasting cycling performance. Also, the prepared electrode could be used as a freestanding electrode in flexible devices at different bending angles. The obtained cyclic voltammetry curves showed negligible changes, indicating the high stability and good flexibility of the electrode. Thus, the use of the in situ strategy can lead to the uniform growth of redox-active MOFs or other porous materials on CNFs.

Peptide-linked perylenebisimide and ferrocene dicarboxylic acid conjugates with tunable optoelectronic properties

Peptide linked perylenebisimide and ferrocene dicarboxylic acid conjugates display wonderful and tunable optoelectronic properties.

Bifunctional TiO2 Nanoflower-Induced H4TCBPE Aggregation Enhanced Electrochemiluminescence for an Ultrasensitive Assay of Organophosphorus.

In this work, the aggregation-induced emission ligand 1,1,2,2-tetra(4-carboxylbiphenyl)ethylene (H4TCBPE) was rigidified in the Ti-O network to form novel electrochemiluminescence (ECL) emitter H4TCBPE-TiO2 nanospheres, which acted as an effective ECL emitter to construct an "on-off" ECL biosensor for ultrasensitive detection of malathion (Mal). H4TCBPE-TiO2 exhibited excellent ECL responses due to the Ti-O network that can restrict the intramolecular free motions within H4TCBPE and then reduce the nonradiative relaxation. Moreover, TiO2 can act as an ECL co-reaction accelerator to promote the generation of sulfate radical anion (SO4•-), which interacts with H4TCBPE in the Ti-O network to produce enhanced ECL response. In the presence of Mal, numerous ligated probes (probe 1 to probe 2, P1-P2) were formed and released by copper-free click nucleic acid ligation reaction, which then hybridized with hairpin probe 1 (H1)-modified H4TCBPE-TiO2-based electrode surface. The P1-P2 probes can initiate the target-assisted terminal deoxynucleoside transferase (TdTase) extended reaction to produce long tails of deoxyadenine with abundant biotin, which can load numerous streptavidin-functionalized ferrocenedicarboxylic acid polymer (SA-PFc), causing quenching of the ECL signal. Thus, the ultrasensitive ECL biosensor based on H4TCBPE-TiO2 ECL emitter and click chemistry-actuated TdTase amplification strategy presents a desirable range from 0.001 to 100 ng/mL and a detection limit low to 9.9 fg/mL. Overall, this work has paved an avenue for the development of novel ECL emitters, which has opened up new prospects for ECL biosensing.

Incorporated ferrocene-derivatives endow Ni-based MOF with high-performance for electrochemical detection

Metal-organic frameworks (MOFs) exhibit structural diversity and functional tunability, rendering them a versatile platform for a wide range of applications. Specifically, defects or function groups induced by exotic ligands is an efficient strategy to adjust the catalytic performance. In this study, we explore the impact of incorporating ferrocene derivatives into two Ni-based MOFs and examine their suitability as potential glucose sensors. One strategy involves introducing bidentate 1,1′-ferrocenedicarboxylic acid (1,1′-Fc) into the 3D Ni-1,4-benzenedicarboxylic acid MOF (Fc-Ni-BDC) using a simple single-step hydrothermal method. Another approach involves encapsulating ferrocenemethylamine (Fc-NH2) inside the cavity of 2D conductive Ni-HHTP MOF (HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) driven by electrostatic attraction to form Fc-Ni-HHTP. On account of the synergy between ferrocene derivatives and MOFs, the hybrid MOFs demonstrated remarkable electrochemical performance, characterized by pronounced electrocatalytic reactivity towards glucose oxidation. It is showed that the doped ferrocene derivatives act as electron donors to the MOF active sites, modifying the electronic structure and facilitating the kinetics of the reactions, then an augmentation in the catalytic efficiency has been achieved. This work demonstrates a simple strategy to improve MOF-based electrochemical sensors by incorporating metallocene ligands.