12093-10-6Relevant articles and documents
PLASTIC PHASE OF FORMYLFERROCENE STUDIED BY X-RAY DIFFRACTION AND MOSSBAUER SPECTROSCOPY.
Sato,Iwai,Sano,Konno
, p. 634 - 638 (1984)
The structures of both the crystal and the plastic phases of formylferrocene have been determined to be orthorhombic by single-crystal X-ray diffraction. The structural change proposes a mechanism of the transition that postulates the translational molecular motion along the a-axis. Moessbauer spectra observed in the plastic phase show little fluctuation of the electric field gradient ascribed to the orientational disorder between x, y, and z axes of the molecule.
α-Cyanoarylethene ferrocene based rod-shaped compounds, synthesis, self-assembly and redox-responsive properties
Tao, Yuan,Chang, Qing,Ding, Wei,Sun, Yue-Yu,Ma, Tao,Cheng, Xiao-Hong
, (2021)
A series of novel α-cyanoarylethene ferrocene based rod-shaped compounds consisting of a biphenyl rigid core, connected with multi-alkyl chain substituted benzene unit via ether (–OCH2-) or ester (-OOC-) link at one end, and with ferrocene unit through α-cyano arylethene at the other end were prepared via Suzuki coupling and Knoevenagel condensation reactions as key steps. The effects of the length and number of the alkyl chain as well as the linking groups on the self-assembly properties of these compounds in bulk states and in organic solutions were investigated. In bulk sate, only the single tetradecyl chain compound with ester (-OOC-) link can show liquid crystalline property, while in organic solvents, such compounds can self-assemble into gels with interesting morphologies. Cyclic voltammetry (CV) and Ultraviolet-visible (UV–vis) absorption studies demonstrated redox characteristics of the prepared compounds. Most interesting is the PEG (polyethylene glycol) film containing such compound (1–5%) was observed to be redox sensitive. The color of the prepared film could be regulated by the redox stimulation, indicating such PEG film have potential for high density information storage.
β-Ferrocenyl-β-amino alcohols: a new class of central chiral ferrocene derivatives
Catasús, Mònica,Bueno, Agustí,Moyano, Albert,Maestro, Miguel A,Mahía, José
, p. 212 - 226 (2002)
An efficient procedure for the enantioselective synthesis of β-ferrocenyl-β-amino alcohols, a new class of central chiral ferrocene derivatives suitable for the elaboration of auxiliaries and ligands for asymmetric synthesis, is described. Key steps of the method are the catalytic asymmetric dihydroxylation of 1-ferrocenyl alkenes and the regio- and stereoselective azide substitution of the hydroxyl group adjacent to the ferrocene moiety. The stereochemistry of the substitution step has been established by X-ray diffraction analysis of a cyclic derivative. The first catalytic enantioselective synthesis of a β-ferrocenyl-β-amino acid derivative is also disclosed.
Chromogenic, Fluorescent, and Redox Sensors for Multichannel Imaging and Detection of Hydrogen Peroxide in Living Cell Systems
Ni, Yue,Liu, Hong,Dai, Di,Mu, Xiqiong,Xu, Jian,Shao, Shijun
, p. 10152 - 10158 (2018)
Hydrogen peroxide (H2O2) is an important reactive oxygen species (ROS). Maintaining the H2O2 concentration at a normal level is critical to achieve the normal physiological activities of cells, which otherwise might trigger various diseases. Therefore, it is necessary to develop new and practical multisignaling sensors for both visualization of intracellular H2O2 and accurate detection of extracellular H2O2. In this paper, a novel multichannel signaling fluorescence-electrochemistry combined probe 1 (FE-H2O2) is presented for imaging and detection of H2O2 in living cell systems. In our design, the probe FE-H2O2 consists of a H2O2 reaction site and 4-ferrocenyl(vinyl)pyridine unit which affords chromogenic, fluorescent, and electrochemical signals. These structural motifs yield a combined chromogenic, fluorescent, and redox sensor in a single molecule. Probe FE-H2O2 showed a Turn-On fluorescence response to H2O2, which can be used for monitoring intracellular H2O2 in vivo. Furthermore, the electrochemical response of probe FE-H2O2 was decreased after the addition of H2O2, which can be applied for accurate detection of H2O2 released from living cells. When the fluorescence imaging method is combined with electrochemical analysis technology, it is hopeful that the well-designed multimodule probe can serve as a practical tool for understanding the metabolism and homeostasis of H2O2 in a complex biological system.
A DFT-Elucidated comparison of the solution-phase and SAM electrochemical properties of short-chain mercaptoalkylferrocenes: Synthetic and spectroscopic aspects, and the structure of Fc- CH2CH2-S-S-CH2CH2-Fc
Lewtak, Jan P,Landman, Marilé,Fernández, Israel,Swarts, Jannie C
, p. 2584 - 2596 (2016)
Facile synthetic procedures to synthesize a series of difficult-To-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(n5-C5H5)(n5-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group Pi. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 pa a radical, Fc(CH2)nS, with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S- (CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group E = Epa,monomer - Epc,dimer ≤ 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. 1H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-Assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, δE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-Thioether, Fc(CH)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while the rate of heterogeneous electron transfer between SAM substrate and electrode was the fastest for the shortest chain derivative, Fc-CH2-S-Au.
Synthesis, characterization, and electronic properties of novel Fc-DCM conjugated system; Experimental and computational studies
Teimuri-Mofrad, Reza,Rahimpour, Keshvar,Ghadari, Rahim
, p. 14 - 19 (2016)
Novel Fc-DCM conjugated compound, 2-(2-ferrocenylvinyl-6-methyl-4H-pyran-4-ylidine) malononitrile, in the form of donor-spacer-acceptor dyad has been synthesized by Knoevenagel condensation. 1H and 13C NMR, FT-IR, CHN analysis and along with atomic absorption spectroscopy supported the predicted structure of the product. The electrochemical behaviour of synthesized compound and the electronic absorption spectra were studied in a variety of solvents. Extensive calculations with various combinations of functionals were carried out to compute energy gap (Eg) of ferrocene derivative. The combined functional and basis set approach PBE/6-31+G(d,p) was found to be well-behaved in the calculation of energy gap. B3LYP/6-31G(d) method was applied to do TD-DFT calculations due to its good agreement with experimental data for prediction of UV-Vis spectra.
New synthesis of ferrocene monocarboxylic acid and systematic studies on the preparation of related key-intermediates
Neto, Alberto Federman,Miller, Joseph,De Andrade, Vania Faria,Fujimoto, Susana Yumi,De Freitas Afonso, Marcia Maisa,Archanjo, Fernando Costa,Darin, Vitor Andre,Andrade E Silva, Marcio Luis,Borges, Aurea Donizete Lanchote,Del Ponte, Gino
, p. 209 - 216 (2002)
An improved technique for the preparation of ferrocenecarboxaldehyde and two new methods for the synthesis of ferrocenemonocarboxylic acid from the aldehyde or from acetyl ferrocene are described. Using the aldehyde or the monocarboxylic acid as starting materials, some important ferrocene key intermediates were prepared: monochlorocarbonyl ferrocene, alkali metal and ammonium ferrocenoates, ferrocene carboxyaldehyde diethylacetal, ferrocenecarboxamide, et..., as well as a new ferrocene derivative: piperazinium diferrocenoate.
Site-selective cation-π interaction as a way of selective recognition of the caesium cation using sumanene-functionalized ferrocenes
Kasprzak, Artur,Sakurai, Hidehiro
, p. 17147 - 17152 (2019)
The first sumanene-ferrocene probes for efficient and selective caesium cation (Cs+) recognition are reported. The working mechanism of the sumanene moiety as the sensing unit was based on the site-selective cation-π interaction in its neutral state. The interactions with Cs+ were characterized by high association constant values together with low limits of detection.
Simultaneous Construction of Planar and Central Chiralities as Well as Unprecedented Axial Chirality on and around a Ferrocene Backbone
Li, Hongjie,Jia, Peijing,Qian, Naixin,Li, Shasha,Jiao, Peng
, p. 2817 - 2828 (2019)
Simultaneous generation of planar, central and axial chiralities on and around a ferrocene backbone via a d-phenylglycinol-induced intramolecular iminium cyclization was disclosed, which is rare and differs from known methods. A series of chiral spiro[cyclopentadienyl-1,2,3,3a-tetrahydropentalenyliron(II)-1,2′-pyrrolidine] derivatives were prepared acording to the new method, and their structures were characterized unambiguously. The axial chirality caused by the ferrocene backbone and the rigid spiral structure was verified by NOESY and variable-temperature NMR experiments and single-crystal XRD analyses. Mechanism for the stereoselective iminium cyclization reaction was suggested, which was influenced by steric hindrance and hydrogen bonding.
Light-Triggered Metal Coordination Dynamics in Photoswitchable Dithienylethene-Ferrocene System
Adarsh, Nayarassery N.,Karmakar, Manisha,Mondal, Bijan,Pal, Adwitiya,Thakur, Arunabha
, p. 6086 - 6098 (2021)
The C2-symmetric photochromic molecule 3, containing dithienylethene (DTE) and ferrocene units connected by an alkyne bridge, represents a unique probe where a metal (Hg2+) binds with the central DTE moiety. Both photoisomerized states of 3 (open, 3o; closed, 3c) are found to interact with Hg2+ ion by the S atoms of the DTE core; however, the binding constants (from a UV-vis study) and DFT calculations suggest that the open isomer (3o) binds with the metal ion more strongly than that of the closed isomer (3c). Notably, the course of metal binding does not perturb the inherent photoisomerization properties of the DTE core and the photoswitchability persists even in the metal-coordinated form of 3, however, with a comparatively slower rate. The quantum yields for photocyclization (φo→c) and photocycloreversion (φc→o) in the free form are 0.56 and 0.007, respectively, whereas the photocyclization quantum yield in the Hg2+ complexed species is 0.068, 8.2 times lower than the photocyclization quantum yield (φo→c) of free 3o. Thus, the rate of photoisomerization can be modulated by a suitable metal coordination to the DTE core. The dynamics of photoswitchability in the metal-coordinated form of DTE has been explored by experimental means (UV-vis and electrochemical studies) as well as quantum chemical calculations.
