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Heterobimetallic (Fe <sup>II</sup> /Pt <sup>II</sup> )-Based Supramolecular Coordination Complexes Using 1,1′-Ferrocene Dicarboxylate: Self-Assembly and Interaction with Carbon Dots
摘要： The synthesis and characterization of a new pyrazine-based ditopic organoplatinum(II) complex having a bite angle of 180° is reported. The facile and efficient syntheses are described of three discrete neutral Fe(II)/Pt(II) heterobimetallic SCCs with Pt(II) acceptor clips of different binding angles, 0, 120, and 180°. These new SCCs were characterized by multinuclear NMR and mass spectrometry. Electrochemical response of these ferrocene containing self-assembled ensembles was studied using cyclic voltammetry. The diplatinum acceptor organometallic clips significantly quench the fluorescence of highly emitting carbon quantum dots (CD), while the self-assembled macrocycles tend to nullify the quenching effect of the organometallic clips. Interestingly, the inefficient quenching of CD fluorescence by these SCCs was found to be directly related to the angular disposition of the binding sites in the Pt(II) based organometallic clips.
关键词： carbon dots,heterobimetallic,electrochemical response,self-assembly,supramolecular coordination complexes,fluorescence quenching,ferrocene
更新于2025-09-23 15:23:52
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Systematic Modulation of Charge Transport in Molecular Device through Facile Control of Molecule-Electrode Coupling using Double Self-assembled Monolayers Nanowire Junction
摘要： We report a novel solid-state molecular device structure based on double self-assembled monolayers (D-SAMs) incorporated into the suspended nanowire architecture to form “Au | SAM-1 || SAM-2 | Au” junction. Using commercially available thiol molecules that are devoid of synthetical difficulty, we constructed Au | S-(CH2)6-Ferrocene || SAM-2 | Au junction, with various length and chemical structure of SAM-2 to tune the coupling between ferrocene conductive molecular orbital and electrode of the junction. Combining low noise and wide temperature range measurement, we demonstrated systematically modulated conduction depending on the length and chemical nature of SAM-2. Meanwhile, transport mechanism transition from tunneling to hopping, and the intermediate state accompanied by the current fluctuation due to the coexistence of the hopping and tunneling transport channels, were observed. Considering the versatility of this solid-state D-SAMs in modulating the electrode-molecule interface and electroactive groups, this strategy thus provides a novel facile strategy for tailorable nanoscale charge transport study and functional molecular devices.
关键词： charge transport,molecular device,nanowire junction,self-assembled monolayers,ferrocene
更新于2025-09-23 15:21:01
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Synthesis, crystal structure analysis, spectral characterization and nonlinear optical exploration of potent thiosemicarbazones based compounds: A DFT refine experimental study
摘要： The thiosemicarbazones have exciting biological and nonlinear optical (NLO) applications. The present study reports detail experimental and computational studies of three novel ferrocene-substituted thiosemicarbazones: (E/Z)-4-(4-chlorobenzyl)-1-(1-ferrocenyl-ethyl)thiosemicarbazone (2) and (E/Z)-4-benzyl-1-(1-ferrocenylethyl)thiosemicarbazones (1) and (E/Z)-4-(2-bromo benzyl)-1-(1-ferrocenylethyl)thiosemicarbazone (3). These compounds were synthesized and resolved into their single crystal structures for the estimation of unit cells, space groups, bond angles and bond lengths. Chemical structures of 1–3 were further characterized spectroscopically employing nuclear magnetic resonance technique (1H NMR), infrared (FT-IR), mass and UV–Visible studies. Computational studies of 1–3 were performed using density functional theory (DFT) tools at M06 level of theory and 6–31 + G(d,p) basis set combination to gain the optimized geometry. A good correlation was found between experimental SC-XRD structures and DFT optimized geometries. Electronic properties including natural bond orbital (NBO) analysis, frontier molecular orbitals (FMOs) analysis, spectroscopic FT-IR data and NLO properties were calculated using same M06/6–31 + G(d,p) level of theory. NBO analysis confirmed the formation of charge separation state due to successful migration of electrons from donor to acceptor unit through π-bridge. Global reactivity parameters were estimated using energies of FMOs which described that 1–3 are chemically hard and stable molecules. Vertical electronic transition states were calculated using time-dependent DFT (TDDFT) at same level of theory. NLO properties of 1–3 were computed 5.77, 3.48 and 8.93 times greater than the standard urea molecule respectively. Two-state model confirmed the potential of synthesized molecules as NLO candidates.
关键词： Frontier molecular orbital,Ferrocene-substituted thiosemicarbazones,Spectroscopic data,Crystal structures,Non-linear optical properties,Density functional theory
更新于2025-09-23 15:21:01
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Electrochemical Immunosensor for Human IgE Using Ferrocene Self-Assembled Monolayers Modified ITO Electrode
摘要： The immunoglobulin E (IgE) level in serum is an important factor in the examination of allergy. Ferrocene (Fc)-modified self-assembled monolayers (SAMs) were placed on an indium tin oxide (ITO) electrode as a sensing layer for the detection of human IgE. The Fc moiety in the SAMs facilitated the electron transfer through the organic SAMs layer and electrocatalytic signal amplification. The electrochemical measurement was accomplished after the sandwich type immobilization of the receptor antibody, target human IgE, and enzyme conjugated secondary antibody. The enzyme product, p-aminophenol, was quantitatively analyzed by redox cycling via Fc. In addition, the electrochemical impedance spectroscopy (EIS) was investigated for the detection of IgE. The limit of detection (LOD), limit of quantification (LOQ), and dynamic range of the electrochemical sensor were 3 IU/mL, 10 IU/mL, and from 10 IU/mL to 100 IU/mL, respectively.
关键词： electrocatalytic reaction,indium tin oxide (ITO),human immunoglobulin E,electrochemical impedance spectroscopy,ferrocene
更新于2025-09-23 15:19:57
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Ferrocene Linkage Facilitated Charge Separation in Conjugated Microporous Polymers
摘要： Conjugated microporous polymers (CMPs) have full access to the organic synthesis toolbox and feature-rich functionality, structural diversity, and high surface area. We incorporated ferrocene (Fc) into the backbones of CMPs and systematically engineered their optical energy gaps. Compared with the CMPs without Fc units yet adopting similar molecular orbital level, Fc-based CMPs can sufficiently generate reactive oxygen species (ROS) under visible light. The resultant ROS are able to effectively decompose the absorbed pollutants, including organic dyes and chemical warfare agents. Specifically, Fc-based CMPs significantly outperform commercial TiO2 (P25) in the degradation of methylene blue and are capable of converting 2-chloroethyl ethyl sulfide (a mustard gas simulant) into completely nontoxic product.
关键词： conjugated microporous polymer,charge separation,photocatalytic degradation,ferrocene,reactive oxygen species
更新于2025-09-19 17:15:36
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Electronic transfer mechanism in self-assembled monolayers of silicon
摘要： This work presents a theoretical-experimental study on electronic transfer mechanism on crystal silicon surface modified with redox molecules derived from ferrocene. The surface modification consists in the reaction of hydrogenated silicon with decyl bromide (10-bromo-1-decene) activated with white light, and its subsequent reaction with monolithio-ferrocene. The samples were analyzed by X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The layers formed are electrochemically active and present a quasi-reversible electrochemical process which is attributed to the ferrocene molecules bound to the silicon surface. In the experimental results, we found an apparent discrepancy, with respect to the results of the cyclic voltammetry, indicating that the redox centers have a diffusive behavior, like to molecules in solution, in spite of these molecules are linked to the silicon surface. While another technique indicates that these redox centers could be attached to the substrate. To understand these results, we have formulated a phenomenological model, based on a cellular automaton, that describes the mechanism of electronic transfer in molecules attached to the substrate. The parameters of the model are obtained from calculations of first principles, based on the density functional theory (DFT). Our results show that the electronic transfer mechanism is influenced by the movement of the redox centers of the molecules attached to the substrate. The latter would explain the apparent discrepancy in the experimental results.
关键词： Silicon,Ferrocene,Surface modification,Electronic transfer
更新于2025-09-11 14:15:04
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Bionic SiO2@Fc(COCH3)2 Core-Shell Nanostructure for Enhancing the Electrochromic Properties of Ferrocene
摘要： Although the properties of electrochromic materials (ECMs) have been enhanced using fabricated porous materials, the effect of materials porosity on such an enhancement remains unclear. Here, we report a novel ECMs with an adjustable pore hierarchy based on quasi-amorphous and ordered arrays of SiO2@Fc(COCH3)2. ECMs with different pore systems were generated by modifying Fc(COCH3)2 concentration and self-assembly temperature. The composition and core-shell structure of the SiO2@Fc(COCH3)2 nanospheres were confirmed through scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FT-IR) and EDX mapping. The influence of adjustable pore system on the electrochemical behavior was studied. Experimental results showed that the current density of the redox couple peaks of the quasi-amorphous porous SiO2@Fc(COCH3)2 films are considerably lower than those of the ordered porous films but are higher than those of the dense Fc(COCH3)2 films. At 550 nm, the transmittance variation of the quasi-amorphous porous SiO2@Fc(COCH3)2 film is 19 %, whereas that of the ordered porous film is 35 %. The coloration and bleaching times of the quasi-amorphous porous SiO2@Fc(COCH3)2 film are 17.1 s and 4.5 s, respectively, whereas those of the ordered porous film are only 16.5 s and 3.5 s, respectively. Furthermore, the porosities of the films are solved numerically by the finite-element method. For the ordered porous SiO2@Fc(COCH3)2 film, the porosity is 0.26, while the quasi-amorphous film became larger (0.31～ 0.41). This work is the first step in combining ferrocene derivative and colloidal crystal porous structures to develop a green, simple and efficient electrochromic process.
关键词： electrochromism,adjustable porosity,colloidal crystals,ferrocene derivatives,core-shell structure
更新于2025-09-09 09:28:46
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Photoinduced mechanical motions of biferrocene-containing pseudorotaxane crystals
摘要： This study presents photoresponsive, dynamic pseudorotaxane crystals composed of axle molecules containing biferrocene or ferrocene groups threaded through a dibenzo[24]crown-8 ether ring. A biferrocene-containing pseudorotaxane crystal is used for photomechanical conversion under 445-nm laser irradiation and provides a lifting force that is 2900 times the weight of the crystal itself.
关键词： photomechanical conversion,biferrocene,ferrocene,photoresponsive,pseudorotaxane
更新于2025-09-09 09:28:46
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Enhanced Signal Amplification in a TLR-4 Biosensor Utilizing Ferrocene-Terminated Mixed Monolayers
摘要： A major challenge in effectively treating infections is to provide timely diagnosis of a bacterial or viral agent. Current cell culture methods require >24 hours to identify the cause of infection. The Toll-Like Receptor (TLR) family of proteins can identify classes of pathogens and has been shown to work well in an impedance-based biosensor, where the protein is attached to an electrode via a self-assembled monolayer (SAM). While the sensitivity of these sensors has been good, they contain a high resistance (>1 kΩ) SAM, generating relatively small signals and requiring longer data collection, which is ill-suited to implementation outside of a laboratory. Here, we describe a novel approach to increase the signal magnitude and decrease the measurement time of a TLR-4 biosensor by inserting a redox-active ferrocenyl-terminated alkane thiol into a mixed SAM containing hydroxyl- and carboxyl-terminated alkane thiols. The SAM formation and modification was confirmed via contact angle and X-ray photoelectron spectroscopy measurements, with TLR-4 immobilization demonstrated through a modified immunosorbent assay. It is shown that these TLR-4 biosensors respond selectively to their intended target, Gram-negative bacteria at levels between 100 and 105 lysed cells/mL, while remaining insensitive to Gram-positive bacteria or viral particles at up to 105 particles/mL. Furthermore, the signal enhancement due to the addition of ferrocene decreased the measurement time to less than one minute and has enabled this sensor to be used with an inexpensive, portable, handheld potentiostat that could be easily implemented in field settings.
关键词： TLR-4,Toll-Like Receptor biosensor,Gram-negative bacteria,ferrocene.,Mixed self-assembled monolayers
更新于2025-09-04 15:30:14