Electronic communication through the ureylene bridge: spectroscopy, structure and electrochemistry of dimethyl 1′,1′-ureylenedi(1-ferrocenecarboxylate)

Mahmoud, Khaled A.; Long, Yi Tao; Schatte, Gabriele; Kraatz, Heinz‐Bernhard

doi:10.1016/j.jorganchem.2004.04.016

Cited by 22 publications

(14 citation statements)

References 29 publications

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“…[54][55][56][57][58] Potentially conducting wires have been obtained by doping the oligoferrocene amides. Electronic interaction across the amide bridge is feasible, as shown by analysis of well-defined mixed-valent systems similar to urea-bridged ferrocenes [59] and in contrast to anhydride-bridged systems. [60] According to modelling studies full charging should unfold the zigzag conformations of the oligoferrocene amides to give extended systems (mechanoelectrical motion, "electrochemically powered artificial muscle").…”

Section: Resultsmentioning

confidence: 99%

Oligonuclear Ferrocene Amides: Mixed‐Valent Peptides and Potential Redox‐Switchable Foldamers

Siebler

Linseis

Gasi

et al. 2011

Chemistry A European J

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Trinuclear ferrocene tris-amides were synthesized from an Fmoc- or Boc-protected ferrocene amino acid, and hydrogen-bonded zigzag conformations were determined by NMR spectroscopy, molecular modelling, and X-ray diffraction. In these ordered secondary structures orientation of the individual amide dipole moments approximately in the same direction results in a macrodipole moment similar to that of α-helices composed of α-amino acids. Unlike ordinary α-amino acids, the building blocks in these ferrocene amides with defined secondary structure can be sequentially oxidized to mono-, di-, and trications. Singly and doubly charged mixed-valent cations were probed experimentally by Vis/NIR, paramagnetic ¹H NMR and Mössbauer spectroscopy and investigated theoretically by DFT calculations. According to the appearance of intervalence charge transfer (IVCT) bands in solution, the ferrocene/ferrocenium amides are described as Robin-Day class II mixed-valent systems. Mössbauer spectroscopy indicates trapped valences in the solid state. The secondary structure of trinuclear ferrocene tris-amides remains intact (coiled form) upon oxidation to mono- and dications according to DFT calculations, while oxidation to the trication should break the intramolecular hydrogen bonding and unfold the ferrocene peptide (uncoiled form).

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Section: Resultsmentioning

confidence: 99%

Oligonuclear Ferrocene Amides: Mixed‐Valent Peptides and Potential Redox‐Switchable Foldamers

Siebler

Linseis

Gasi

et al. 2011

Chemistry A European J

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“…Several older reports are concerned with the formation of the parent Fc–CO–O–CO–Fc anhydride 17. However, in contrast to the ureylene‐bridged “head–head” dimer of Fca11 and “head–tail” amides of Fca,10a,12,13 structural, conformational, and electrochemical data of bis(Fca anhydrides) are lacking in the literature.…”

Section: Introductionmentioning

confidence: 99%

“…With asymmetrical 1,1′‐disubstituted ferrocenes, e.g. 1′‐aminoferrocene‐1‐carboxylic acid (Fca),10 several linkages are conceivable, which should lead to different communication channels.In “dimers” of Fca, a symmetrical ureylene bridge MeOOC–Fn–NH–CO–NH–Fn–COOMe (“head–head dimer”),10b,11 an asymmetrical amide bridge (“head–tail dimer”),10a,12,13 and a symmetrical anhydride bridge (“tail–tail” dimer) can be formed (Fn = 1,1′‐disubstituted ferrocene) (Scheme ). The different number, type, and hybridization of the bridging atoms (2–3; C, N, O atoms; formal sp 2 , sp 3 ) and the preferred relative orientations of the ferrocene units are believed to modulate the communication pathways.…”

Section: Introductionmentioning

confidence: 99%

“…The different number, type, and hybridization of the bridging atoms (2–3; C, N, O atoms; formal sp 2 , sp 3 ) and the preferred relative orientations of the ferrocene units are believed to modulate the communication pathways. Urea and amide bridges are reported to promote communication between the ferrocene subunits 11–13. In Kraatz's amide‐bridged [Fca‐Ala] oligomers with intervening α‐amino acids between the ferrocene units, electronic communication is not expected because of the blocking alanine moieties 14.…”

Section: Introductionmentioning

confidence: 99%

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“Tail–Tail Dimerization” of Ferrocene Amino Acid Derivatives

2010

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Acid anhydrides of N‐protected 1′‐aminoferrocene‐1‐carboxylic acid (Fca) have been prepared and spectroscopically characterized (protection group Boc, Fmoc, Ac; 4a–4c). The structure of the Boc‐derivative 4a has been determined by single‐crystal X‐ray crystallography. An intramolecular N–H···O hydrogen bond involving the carbamate units results in a ring structure containing the two ferrocene units, the anhydride moiety, and the hydrogen bond. In the crystal, the individual molecules are connected by intermolecular N–H···O hydrogen bonds of the carbamate unit. Experimental and theoretical studies suggest that the ring motif is also a dominant species in solution. Electronic communication across the anhydride moiety is found to be very weak as judged from electrochemical, spectroscopic, and theoretical experiments.

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“…The synthesis of ferrocene-peptide systems has garnered attention by several groups and has led to a library of asymmetric peptide-ferrocene systems. 46,[48][49][50][51][52] The work described herein details the synthesis of the first asymmetric ferrocene bio-conjugates containing biotin-ferrocene-cysteine. This compound serves as a model through which other small molecule receptors could be considered for detection of biologically relevant molecules.…”

Section: Discussionmentioning

confidence: 99%

Synthetic Methodology for Asymmetric Ferrocene Derived Bio-conjugate Systems via Solid Phase Resin-based Methodology

Scarborough

González

Rodich

et al. 2015

JoVE

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Early detection is a key to successful treatment of most diseases, and is particularly imperative for the diagnosis and treatment of many types of cancer. The most common techniques utilized are imaging modalities such as Magnetic Resonance Imaging (MRI), Positron Emission Topography (PET), and Computed Topography (CT) and are optimal for understanding the physical structure of the disease but can only be performed once every four to six weeks due to the use of imaging agents and overall cost. With this in mind, the development of "point of care" techniques, such as biosensors, which evaluate the stage of disease and/or efficacy of treatment in the clinician's office and do so in a timely manner, would revolutionize treatment protocols.1 As a means to exploring ferrocene based biosensors for the detection of biologically relevant molecules 2 , methods were developed to produce ferrocene-biotin bio-conjugates described herein. This report will focus on a biotin-ferrocenecysteine system that can be immobilized on a gold surface. Video LinkThe video component of this article can be found at

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Electronic communication through the ureylene bridge: spectroscopy, structure and electrochemistry of dimethyl 1′,1′-ureylenedi(1-ferrocenecarboxylate)

Cited by 22 publications

References 29 publications

Oligonuclear Ferrocene Amides: Mixed‐Valent Peptides and Potential Redox‐Switchable Foldamers

Oligonuclear Ferrocene Amides: Mixed‐Valent Peptides and Potential Redox‐Switchable Foldamers

“Tail–Tail Dimerization” of Ferrocene Amino Acid Derivatives

Synthetic Methodology for Asymmetric Ferrocene Derived Bio-conjugate Systems via Solid Phase Resin-based Methodology

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