Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and <i>n</i>-Butylferrocene: A UV–vis Matrix-Isolation Study

Pinelo, Laura F.; Kugel, Roger W.; Ault, Bruce S.

doi:10.1021/acs.jpca.5b07292

Cited by 14 publications

(8 citation statements)

References 29 publications

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“…Considering its low oxidation potential, ferrocene can also be advantageously used as an electron donor to form charge transfer complexes by intermolecular interaction with the appropriate electron acceptor. In the literature, numerous charge transfer complexes obtained by opposing ferrocene to tetracyanoethylene, [268] ozone, [269] polyiodomethanes, [270] tetranitromethane, [271] iodine, 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and p-chloranil [272] have notably been reported. Considering the propensity of ferrocene to form intermolecular charge transfer complexes (CTCs), the possibility to initiate a free radical polymerization (FRP) of acrylates with ferrocene-alkyl/aryl halide CTCs was examined.…”

Section: Free Radical Polymerization Via Ferrocene-alkyl/aryl Chloridmentioning

confidence: 99%

Recent advances on ferrocene-based photoinitiating systems

Dumur

2021

European Polymer Journal

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Photoinitiators of polymerization with reversible electrochemical properties are actively researched as these molecules can advantageously be used in photocatalytic systems, enabling to reduce the photoinitiators content within the photocurable resins. In this field, ferrocene which is extensively used by electrochemists as a reference compound for cyclic voltammetry also exhibits a significant absorption in the visible range as well as a low oxidation potential so that this metallocene was used as a potential candidate for the design of photoinitiators of polymerization. Over the years, ferrocene has been examined in numerous polymerization processes going from anionic to cationic polymerizations, but also for the freeradical polymerization of acrylates or as a sacrificial electron donor in free radical polymerization processes. Parallel to this, the development of cheap, compact and energysaving irradiation setups based on light-emitting diodes (LEDs) have clearly favored the development of visible light photoinitiators and this technology has nowadays the potential to replace the well-established UV photopolymerization. In this review, an overview of the recent development of the ferrocene-based photoinitiating systems is provided. To evidence the interest of the ferrocene derivatives recently developed, comparisons with benchmark photoinitiators will be provided.

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Section: Free Radical Polymerization Via Ferrocene-alkyl/aryl Chloridmentioning

confidence: 99%

Recent advances on ferrocene-based photoinitiating systems

Dumur

2021

European Polymer Journal

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“…Regarding the C 2 H 4 -O 3 system, we could not observe photoproducts spectroscopically upon irradiation at 405 nm, and there might be a "gap" in the CT band around this wavelength, whereas no such depletion of photolysis was found for other olefins. The observation of CT bands has been reported for some organic molecule-ozone complexes [4][5][6][7]. Jonnalagadda et al measured the CT band for the C 2 H 4 -O 3 complex in the Xe matrix [6].…”

Section: Discussionmentioning

confidence: 82%

“…The key reactants for the oxidation processes are ozone (O 3 ), hydroxyl (OH), and nitrate (NO 3 ) radicals. Ozone forms charge-transfer (CT) complexes with various organic molecules, and exhibits strong CT bands in the ultraviolet-visible (UV-VIS) region [4][5][6][7]. The oxidation processes involve reactions in both light and dark conditions; therefore, it is important to understand how light-induced oxidation proceeds in the olefin-ozone system.…”

Section: Introductionmentioning

confidence: 99%

Observation of Light-Induced Reactions of Olefin–Ozone Complexes in Cryogenic Matrices Using Fourier-Transform Infrared Spectroscopy

Ito

2022

Photochem

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Each olefin (ethylene, trans-1,3-butadiene, isoprene, dimethyl butadiene (DMB)) and ozone molecules were codeposited on a CsI window at cryogenic temperature, and the products of photolysis with ultraviolet–visible light were observed using Fourier-transform infrared spectroscopy. The products of the C2H4–O3 system could be assigned to glyoxal (CHO–CHO), ethylene oxide (c–C2H4O), CO, and CO2. The formation of CHO–CHO and c–C2H4 and the absence of H2CO and HCOOH indicated that the main reaction channels did not involve C–C bond breaking. Based on this simple scheme, the photoproducts of different olefin–O3 systems were assigned, and the vibrational features predicted by density functional theory calculations were compared with the observed spectra. Regarding butadiene, spectral matches between the observations and calculations seemed reasonable, while assignments for isoprene ambiguities of and DMB remain, mainly because of the limited availability of authentic sample spectra.

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“…23 Evidence for the formation of these charge transfer complexes was based on the green color, suggesting strong red and blue absorptions in the visible spectrum, and slightly red-shifted ozone absorptions that are characteristic of perturbed ozone. 30 Recently, a UV-vis study 31 , and (c) (1570-1700 cm -1 ) of: Ar/ 16 O 3 /n-butylferrocene matrix after 1 hour red (λ ≥ 600 nm) irradiation (red trace), dark deposited Ar/ 16 O 3 / nbutylferrocene (green trace), Ar/ n-butylferrocene (black trace), Ar/ 16 O 3 (pink trace), and Ar/ 18 O 3 /n-butylferrocene after 30 min. red (λ ≥ 600 nm) irradiation (blue trace).…”

Section: Resultsmentioning

confidence: 99%

Long wavelength photochemistry of ozone and n-butylferrocene: A matrix isolation study

Pinelo

Ault

2016

Journal of Molecular Structure

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The photochemical reaction of ozone and n-butylferrocene has been studied using a combination of argon-matrix isolation, infrared spectroscopy, and theoretical calculations. The dark deposition produced a vivid green matrix that, when irradiated with red light, turned a brownish-red color.This green matrix as well as slightly red-shifted O 3 infrared absorptions are indicative of the formation an initial charge transfer complex between ozone and nbutylferrocene. The spectral resultssupport the photodissociation of the complexed ozone with red light (λ ≥ 600 nm) producing an oxygen atom, O(3 P), and a dioxygen molecule, O 2 (3 Σ). The O(3 P) then reacts with n-butylferrocene to form products consisting of an iron atom with a coordinated n-butylcyclopentadienyl or cyclopentadienyl ring and either: (1) a pyran, (2) an aldehyde, or (3) a bidentate cyclic aldehyde with a seven-membered ring including the iron atom. The photochemical products were characterized with FT-IR spectroscopy, 18 O-labeled O 3 experiments, and DFT calculations using the B3LYP functional with the 6-311++G(d,2p) basis set. A possible mechanism for the photochemical reaction is discussed.

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Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and n-Butylferrocene: A UV–vis Matrix-Isolation Study

Cited by 14 publications

References 29 publications

Recent advances on ferrocene-based photoinitiating systems

Recent advances on ferrocene-based photoinitiating systems

Observation of Light-Induced Reactions of Olefin–Ozone Complexes in Cryogenic Matrices Using Fourier-Transform Infrared Spectroscopy

Long wavelength photochemistry of ozone and n-butylferrocene: A matrix isolation study

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