Synthesis, electrochemistry and IR spectroelectrochemistry of bisferrocenyl bridged benzene derivates

Huang, Peng; Jin, Baokang; Liu, Peng; Cheng, Longjiu; Wei, Cheng; Zhang, Shengyi

doi:10.1016/j.jorganchem.2011.10.019

Cited by 13 publications

(3 citation statements)

References 24 publications

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“…25,66 The dibromo/diiodo heteroaromatic precursors for 3−7 were prepared as reported previously. 40,67,68,75 The syntheses of 2− The IR spectra of the bis(ferrocenylethynyl) complexes show a single, sharp ν(CC) in the 2200−2010 cm −1 range, characteristic of other ethynylferrocenyls 42,43,76 containing aromatic and heteroaromatic spacer groups. The 1 H NMR spectra showed a characteristic pattern of singlet and triplet absorption at ∼4 ppm for the unsubstituted and substituted cyclopentadienyl protons, respectively.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Long-Range Intramolecular Electronic Communication in Bis(ferrocenylethynyl) Complexes Incorporating Conjugated Heterocyclic Spacers: Synthesis, Crystallography, and Electrochemistry

et al. 2013

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A new series of bis(ferrocenylethynyl) complexes, 3-7, and a mono(ferrocenylethynyl) complex, 8, have been synthesized incorporating conjugated heterocyclic spacer groups, with the ethynyl group facilitating an effective long-range intramolecular interaction. The complexes were characterized by NMR, IR, and UV-vis spectroscopy as well as X-ray crystallography. The redox properties of these complexes were investigated using cyclic voltammetry and spectroelectrochemistry. Although there is a large separation of ∼14 Å between the two redox centers, ΔE(1/2) values in this series of complexes ranged from 50 to 110 mV. The appearance of intervalance charge-transfer bands in the UV-vis-near-IR region for the monocationic complexes further confirmed effective intramolecular electronic communication. Computational studies are presented that show the degree of delocalization across the Fc-C≡C-C≡C-Fc (Fc = C5H5FeC5H4) highest occupied molecular orbital.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Long-Range Intramolecular Electronic Communication in Bis(ferrocenylethynyl) Complexes Incorporating Conjugated Heterocyclic Spacers: Synthesis, Crystallography, and Electrochemistry

et al. 2013

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“…The IR spectra of the ligand 2 and the complexes 3 – 5 show a single sharp band around 2210 cm –1 characteristic of ν(CC) in ethynylferrocenyls bonded to aromatic and heteroaromatic groups. ,− The ν(CpFc) ring vibration signals changed significantly from ligand 2 (484 cm –1 ) to complexes 3 – 5 (472 cm –1 ), but among the complexes 3 – 5 , this vibration band is independent of the number of ligands coordinated to each Cu center. − The pyridine vibrational modes ν(ring), ν(CCH), and ν(CN) are affected on coordination of the pyridyl ligand to Cu yielding complexes 3 – 5 . , The pyridine ν(CCH) vibrational band shows a lower value (1014 cm –1 ) in complex 3 compared to 2 (1025 cm –1 ), and 4 and 5 (1027 and 1028 cm –1 , respectively).…”

Section: Resultsmentioning

confidence: 99%

New Multi-Ferrocenyl- and Multi-Ferricenyl- Materials via Coordination-Driven Self-Assembly and via Charge-Driven Electro-Crystallization

et al. 2013

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Three new tetra-ferrocenylethynylpyridinyl copper complexes, L4(CuI)4 (3), L4(CuBr)2 (4), and L4(CuCl)2 (5) have been prepared from the reaction of ferrocenylethynylpyridine (L)(2) with copper halides CuX (with X = I(-), Br(-), Cl(-)).The ligand 2 and the complexes 3-5 have been fully characterized by spectroscopic methods. The structures of 2-4 have been confirmed by single-crystal X-ray crystallography. 2 forms a dimer in the crystalline-state through C-H··N hydrogen bonds. 4 and 5 are dimers and 3 a tetramer, in all cases linked through Cu-X··Cu bridging interactions. Cyclic voltammetry in dichloroethane showed chemically reversible multiferrocenyl oxidation signals with evidence for product electro-crystallization. The oxidation products were isolated by electrodeposition onto a Pt disc electrode and investigated by scanning electron microscopy which confirmed the spontaneous formation of crystalline oxidation products with distinctive morphologies. Energy dispersive X-ray elemental analysis shows the presence of hexafluorophosphate (counterion) with the P:Fe ratio of 1:1, 0.5:1, and 1:1 for the electrocrystallized products 3, 4, and 5, respectively, suggesting the formulas [3](4+)(PF6(-))4, [4](2+)(PF6(-))2, and [5](4+)(PF6(-))4 for the electro-crystallized products.

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“…The ferrocene (Fc) is widely used in investigating the intramolecular electron transfers due to its redox activity and electrochemical stability, and the research on intramolecular electron transfers could provide simple and convenient for designing prospective ferrocene-containing molecular wires and conducting polymers [1][2][3][4] . Generally, two or more ferrocenyl units assembled through various conducting spacers to construct molecular models for studying intramolecular electron transfers 5 , the various kind spacers involving of the atom 6 , alkenyl 7 , alkynyl 8 and various aromatic rings 9 . When one of ferrocene unit occur electrochemical oxidize, an intramolecular donor-acceptor system is formed, the charge may be transfer to the other ferrocene units through the spacers, and the spacers' types 10 , structures 11 and chemical properties 12 can in uence the electron transfers capability.…”

Section: Introductionmentioning

confidence: 99%

The Intramolecular Electronic Interaction Regulated by Five-membered Heterocycle Spacer

Han

Wang

2021

Preprint

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The spacer in diferrocenyl derivatives has significant effects on intramolecular electronic interaction properties. In this work, nine diferrocenyl five-membered heterocyclic molecules are synthesized as models to investigate the effect of intramolecular electron-transfer properties systematically, including 2,5-diferrocenyl-1-phenyl-pyrrole (1), 2,5-diferrocenylfuran (2), 2,5-diferrocenylthiophene (3), 2,5-diferrocenyl-1H-imidazole (4), 2,5-diferrocenyloxazole (5), 2,5-diferrocenylthiazole (6), 2,5-diferrocenyl-1,3,4-triazole (7), 2,5-diferrocenyl-1,3,4-oxadiazole (8) and 2,5-diferrocenyl-1,3,4-thiadiazole (9). The molecules were prepared in cyclization reaction and characterized by Elemental analysis, FT-IR, MS and NMR. Moreover, the molecular structures of 2,5-diferrocenylthiazole and 2,5-diferrocenyl-1,3,4-oxadiazole were determined by the single crystal X-ray diffraction. The intramolecular electronic interactions were investigated through cyclic voltammetry in combination with density functional theory (DFT) calculations. The results revealed that the electronic interaction decreased with the increase of heteroatoms in central heterocycle spacer, and the electron-transfer property could be regulated by regulate central heterocycle spacer species.

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Synthesis, electrochemistry and IR spectroelectrochemistry of bisferrocenyl bridged benzene derivates

Cited by 13 publications

References 24 publications

Long-Range Intramolecular Electronic Communication in Bis(ferrocenylethynyl) Complexes Incorporating Conjugated Heterocyclic Spacers: Synthesis, Crystallography, and Electrochemistry

Long-Range Intramolecular Electronic Communication in Bis(ferrocenylethynyl) Complexes Incorporating Conjugated Heterocyclic Spacers: Synthesis, Crystallography, and Electrochemistry

New Multi-Ferrocenyl- and Multi-Ferricenyl- Materials via Coordination-Driven Self-Assembly and via Charge-Driven Electro-Crystallization

The Intramolecular Electronic Interaction Regulated by Five-membered Heterocycle Spacer

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