Research on Ferrocene and Ferrocene-Containing Compounds

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (31 July 2024) | Viewed by 8149

Special Issue Editors


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Guest Editor
Department of Chemistry and Biochemistry, Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, 10000 Zagreb, Croatia
Interests: ferrocene peptides; chiroptical sensing; conformational analysis; chirality transfer; circular dichroism spectroscopy

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Guest Editor
Department of Chemistry and Biochemistry, Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, 10000 Zagreb, Croatia
Interests: ferrocene bioconjugates; organometallic chemistry; conformational analysis; synthesis; peptidomimetics; bioactivity
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Special Issue Information

Dear Colleagues,

With the discovery of ferrocene in 1951 and the deciphering of its aromatic sandwich structure, a new era of the explosive development of organometallic chemistry began. Since then, numerous derivatives of ferrocene, sometimes referred to as the benzene of modern organometallic chemistry, have been synthesized and characterized. Due to its exceptional properties—solubility in common organic solvents, stability, chemical modifiability, reactivity as a super-aromatic electrophile, and redox activity—ferrocene and its derivatives are of great interest in various fields. These include nanotechnology, sensing, optical and redox devices, batteries and other materials, catalysis, especially asymmetric, and medicine. Considering the diversity of the ferrocene derivatives themselves as well as their applications, we invite you to present your achievements and findings in the field of ferrocene chemistry in this Special Issue.

Dr. Mojca Čakić Semenčić
Dr. Lidija Barišić
Guest Editors

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Keywords

  • ferrocene
  • organometallic chemistry
  • synthesis
  • applications
  • bioconjugates
  • conformational analysis
  • structure–activity relationship
  • spectroscopy
  • molecular modeling

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Published Papers (4 papers)

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Research

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10 pages, 2790 KiB  
Article
[1]Ferrocenophane Bridged by a 9-Silafluorenylidene Moiety
by Shinnosuke Usuba, Koh Sugamata, Shogo Morisako and Takahiro Sasamori
Inorganics 2024, 12(3), 66; https://doi.org/10.3390/inorganics12030066 - 22 Feb 2024
Viewed by 1868
Abstract
Sila[1]ferrocenophane bearing a 9-silafluorenylidene moiety (1) as a bridging unit was synthesized and isolated as a stable crystalline compound. Sila[1]ferrocenophane 1, which was newly obtained in this study, was characterized by spectroscopic analyses, a single-crystal X-ray diffraction (SC-XRD) analysis, and [...] Read more.
Sila[1]ferrocenophane bearing a 9-silafluorenylidene moiety (1) as a bridging unit was synthesized and isolated as a stable crystalline compound. Sila[1]ferrocenophane 1, which was newly obtained in this study, was characterized by spectroscopic analyses, a single-crystal X-ray diffraction (SC-XRD) analysis, and electrochemical measurements. Due to the characteristic 9-silafluorenyl moiety, 1 exhibited large electron affinity and a slightly higher oxidation potential relative to that of ferrocene. In addition, 1 was found to undergo ring-opening polymerization (ROP) triggered by thermolysis at a lower temperature relative to that of Ph2Sifc (1′, fc = 1,1′-ferrocenylidene). It also underwent ROP through reduction by KC8 to give the corresponding polymeric compound. The DFT calculations suggested that one-electron reduction of 1 would promote ring-opening polymerization, as shown in the experimental results. Full article
(This article belongs to the Special Issue Research on Ferrocene and Ferrocene-Containing Compounds)
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12 pages, 5641 KiB  
Article
Central-to-Helical-to-Axial Chirality Transfer in Chiroptical Sensing with Ferrocene Chromophore
by Marko Nuskol, Petar Šutalo, Monika Kovačević, Ivan Kodrin and Mojca Čakić Semenčić
Inorganics 2023, 11(6), 225; https://doi.org/10.3390/inorganics11060225 - 24 May 2023
Cited by 2 | Viewed by 1497
Abstract
The effect of attaching the achiral, cyclic 1-aminocyclohexanecarboxylic acid (Ac6c) directly to the aminoferrocene unit (Ac6c−NH−Fc) appears to be a promising route for the development of a new chiroptical sensor based on a ferrocene chromophore. Three new compounds (Boc−AA−Ac6c−NH−Fc; AA = L-Ala, L-Val, [...] Read more.
The effect of attaching the achiral, cyclic 1-aminocyclohexanecarboxylic acid (Ac6c) directly to the aminoferrocene unit (Ac6c−NH−Fc) appears to be a promising route for the development of a new chiroptical sensor based on a ferrocene chromophore. Three new compounds (Boc−AA−Ac6c−NH−Fc; AA = L-Ala, L-Val, L-Phe) were synthesized, spectroscopically characterized (IR, NMR, CD), and conformationally analyzed (DFT). The chiral information was transferred from the L-amino acid to the ferrocene chromophore by the predominant formation of P-helical structures with ten-membered hydrogen-bonded rings (β-turns). The perturbation of the ferrocene chromophore and the appearance of the negative CD signal near 470 nm originates from a relative orientation of the directly linked amide and cyclopentadienyl planes, described by the dihedral angle χ. The sterically demanding Ac6c amino acid makes trans-like configurations more favorable and thus restricts the dihedral angle χ, which then leads to the appearance of the negative peak near 470 nm in the CD curve. Full article
(This article belongs to the Special Issue Research on Ferrocene and Ferrocene-Containing Compounds)
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Review

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22 pages, 2541 KiB  
Review
Molecular Logic Gates Based on Ferrocene-Containing Compounds
by Christina Eleftheria Tzeliou, Konstantinos P. Zois and Demeter Tzeli
Inorganics 2024, 12(4), 106; https://doi.org/10.3390/inorganics12040106 - 6 Apr 2024
Cited by 1 | Viewed by 1634
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Research on Ferrocene and Ferrocene-Containing Compounds)
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28 pages, 7851 KiB  
Review
Ferrocene-Based Electrochemical Sensors for Cations
by Angel A. J. Torriero and Ashwin K. V. Mruthunjaya
Inorganics 2023, 11(12), 472; https://doi.org/10.3390/inorganics11120472 - 4 Dec 2023
Cited by 2 | Viewed by 2246
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Research on Ferrocene and Ferrocene-Containing Compounds)
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