The Synthesis of Substituted Ferrocenes and other π‐Cyclopentadienyl‐Transition Metal Compounds

Bublitz, Donald E.; Rinehart, Kenneth L.

doi:10.1002/0471264180.or017.01

Cited by 5 publications

(3 citation statements)

References 322 publications

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“…Fullerenes C 60 and C 70 , (6,5)-SWCNT (95% purity), and graphene were purchased from Sigma-Aldrich. BODIPY derivative 3 , acetyl ferrocene, and chalcones 3a , 3b , 3c , and 3d were prepared as described earlier. SWCNTs were additionally purified following the literature procedure …”

Section: Experimental Partmentioning

confidence: 99%

1,7-Dipyrene-Containing Aza-BODIPYs: Are Pyrene Groups Effective as Ligands To Promote and Direct Complex Formation with Common Nanocarbon Materials?

et al. 2018

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A series of 1,7-dipyrene-aza-BODIPY and 1,7-dipyrene-3,5-diferrocene-aza-BODIPY derivatives 5a–e with pyrene ligands covalently attached to the β-pyrrolic positions of the boron-azadipyrromethene (aza-BODIPY) core have been prepared and characterized by NMR, UV–vis, and steady-state fluorescence spectroscopy; high-resolution mass spectrometry; and X-ray crystallography. The redox processes of these donor–acceptor aza-BODIPY systems were investigated by electrochemistry (cyclic voltammetry and differential pulse voltammetry methods) and spectroelectrochemistry. The potential of the closely spaced 1,7-dipyrene fragments to promote formation of noncovalent π-complexes with nanocarbon materials (C60, C70, (6,5)-single-walled carbon nanotube, and graphene) was explored. UV–vis, steady-state fluorescent, and time-resolved transient absorption spectroscopy data indicated that the interaction between the new pyrene-aza-BODIPYs and C60 or C70 fullerenes in solution is weak, and time-resolved transient absorption spectroscopy provided no evidence of photoinduced electron transfer. X-ray crystallography on a binary solid of aza-BODIPYs 5b and C60 was indicative of a pyrene–pyrene rather than pyrene–C60 interaction motif, whereas fullerenes were found to form close contacts with the electron-rich B,O-chelated part of aza-BODIPY 5b. In contrast, pyrene–pyrene and pyrene–C60 but not aza-BODIPY–C60 interactions were observed in the crystal structure of aza-BODIPY 5d and C60. Density functional theory (DFT) and time-dependent DFT calculations were used to support conclusions based on experimental data and are suggestive of rather weak interaction energies between 1,7-dipyrene-aza-BODIPYs and nanocarbon materials. Direct comparison with an analogous control compound lacking the pyrene ligands demonstrated that the pyrene substituents were ineffective at promoting and directing complex formation with nanocarbon materials. A common measurement of complex formation, emission loss in the presence of a nanocarbon acceptor, was demonstrated to have an alternative explanation in these systems, and the general effectiveness of using pyrene ligands to build noncovalent complexes was drawn into question.

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Section: Experimental Partmentioning

confidence: 99%

1,7-Dipyrene-Containing Aza-BODIPYs: Are Pyrene Groups Effective as Ligands To Promote and Direct Complex Formation with Common Nanocarbon Materials?

et al. 2018

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“…Ferrocene has been extensively researched, and numerous good reviews for both its organic and inorganic chemistry are available. − Ferrocene reacts in multiple different ways such as Friedel–Crafts acylation and alkylation; furthermore, it can be sulfonated, formylated, and metalated with n -butyllithium. , Research of ferrocene-containing compounds is thriving and is greatly stimulated by their many successful applications, especially in electrochemistry due to the ideal redox behavior of the iron (II/III) couple. , …”

Section: Introductionmentioning

confidence: 99%

Redox and Photophysical Properties of Four Subphthalocyanines Containing Ferrocenylcarboxylic Acid as Axial Ligands

Swarts

Conradie

2020

Inorg. Chem.

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Four new ferrocenylsubphthalocyanines Y-BSubPc, with ferrocenylcarboxylic acid YH = Fc-CH 2 −CH 2 −COOH (1) or Fc-CHCH−COOH (2) in the axial Y position, were synthesized with a 40% yield. The axial ferrocenylcarboxylic acid moiety did not have a significant influence on the position of the Q bands maxima of the UV/vis spectra of the ferrocenylsubphthalocyanines or on the 1 H NMR position of the ring proton peaks of Y-BSubPc(H 12 ) or on the 19 F NMR position of the ring F peaks of YSubPc(F 12 ), relative to their respective parent compounds Cl-BSubPc(H 12 ) 3 and Cl-BSubPc(F 12 ) 4, containing axial chlorine. Very weak metal-to-ligand-charge-transfer bands (MLCT) in the near-IR region were observed. An electrochemical study utilizing cyclic voltammetry showed that electronic communication exists between ferrocene on the axial ferrocenylcarboxylic acid and the π-electrons of the macrocycle of the ferrocenylsubphthalocyanine (Fc(CH 2 ) 2 COO)-BSubPc(H) 12 ,5, (Fc(CH) 2 COO)-BSubPc(H) 12 , 6, (Fc(CH 2 ) 2 COO)-BSubPc(F) 12 , 7, and (Fc(CH) 2 COO)-BSubPc(F) 12 , 8. The Fe group of the ferrocenyl-containing axial ligand is involved in the first reversible oxidation process, followed by a second oxidation localized on the subphthalocyanine ligand. The fluorine ring substituents in SubPcs 7 and 8 caused the ferrocenyl oxidation to shift more positive by ca. 0.1 V, compared to SubPcs 5 and 6 without fluorine. Density functional theory (DFT) calculations provided further insight into the properties of these novel ferrocenylsubphthalocyanines. The neutral species of SubPcs 5−8 have LUMOs with mainly π-ring character and HOMOs with mainly iron-d character, confirming ring-based reduction, metal-based Fe(II) to Fe(III) oxidation, as well as weak MLCT in the near-IR region. Further DFT optimization of the cation (oxidized) species was essential to verify the second ring-based oxidation.

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“…The discovery of ferrocene in 1951 [1] unlocked an entirely new research field and over the years ferrocene has been extensively studied and well-reviewed in organic and inorganic chemistry [2][3][4][5]. The research of ferrocene-containing compounds thrives, and new research keeps on growing due to their varying successful applications.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Spectroscopy, Electrochemistry and DFT of Electron-Rich Ferrocenylsubphthalocyanines

Swarts

Conradie

2020

Molecules

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A series of novel ferrocenylsubphthalocyanine dyads Y-BSubPc(H)12 with ferrocenyl-carboxylic acids Y-H = (FcCH2CO2-H), (Fc(CH2)3CO2-H) or (FcCO(CH2)2CO2-H) in the axial position were synthesized from the parent Cl-BSubPc(H)12 via an activated triflate-SubPc intermediate. UV/Vis data revealed that the axial ferrocenyl-containing ligand did not influence the Q-band maxima compared to Cl-BSubPc(H)12. A combined electrochemical and density functional theory (DFT) study showed that Fe group of the ferrocenyl-containing axial ligand is involved in the first reversible oxidation process, followed by a second oxidation localized on the macrocycle of the subphthalocyanine. Both observed reductions were ring-based. It was found that the novel Fc(CH2)3CO2BSubPc(H)12 exhibited the lowest first macrocycle-based reduction potential (−1.871 V vs. Fc/Fc+) reported for SubPcs till date. The oxidation and reduction values of Fc(CH2)nCO2BSubPc(H)12 (n = 0–3), FcCO(CH2)2CO2BSubPc(H)12, and Cl-BSubPc(H)12 illustrated the electronic influence of the carboxyl group, the different alkyl chains and the ferrocenyl group in the axial ligand on the ring-based oxidation and reduction values of the SubPcs.

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The Synthesis of Substituted Ferrocenes and other π‐Cyclopentadienyl‐Transition Metal Compounds

Cited by 5 publications

References 322 publications

1,7-Dipyrene-Containing Aza-BODIPYs: Are Pyrene Groups Effective as Ligands To Promote and Direct Complex Formation with Common Nanocarbon Materials?

1,7-Dipyrene-Containing Aza-BODIPYs: Are Pyrene Groups Effective as Ligands To Promote and Direct Complex Formation with Common Nanocarbon Materials?

Redox and Photophysical Properties of Four Subphthalocyanines Containing Ferrocenylcarboxylic Acid as Axial Ligands

Synthesis, Spectroscopy, Electrochemistry and DFT of Electron-Rich Ferrocenylsubphthalocyanines

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