Dataset Information

Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO₂ Exposure.

ABSTRACT: Due to its unique magnetic properties offered by the open-shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state. Here, we show that on Cu(100), indeed, the strong hybridization between the Fe d-states of FePc and the sp-band of the copper substrate modifies the charge distribution in the molecule, significantly influencing the magnetic properties of the iron ion. The Fe^II ion is stabilized in the low singlet spin state (S=0), leading to the complete quenching of the molecule magnetic moment. By exploiting the FePc/Cu(100) interface, we demonstrate that NO₂ dissociation can be used to gradually change the magnetic properties of the iron ion, by trimming the gas dosage. For lower doses, the FePc film is decoupled from the copper substrate, restoring the gas phase triplet spin state (S=1). A higher dose induces the transition from ferrous to ferric phthalocyanine, in its intermediate spin state, with enhanced magnetic moment due to the interaction with the atomic ligands. Remarkably, in this way, three different spin configurations have been observed within the same metalorganic/metal interface by exposing it to different doses of NO₂ at room temperature.

SUBMITTER: Cojocariu I

PROVIDER: S-EPMC7898877 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO<sub>2</sub> Exposure.

Cojocariu Iulia I Carlotto Silvia S Sturmeit Henning Maximilian HM Zamborlini Giovanni G Cinchetti Mirko M Cossaro Albano A Verdini Alberto A Floreano Luca L Jugovac Matteo M Puschnig Peter P Piamonteze Cinthia C Casarin Maurizio M Feyer Vitaliy V Schneider Claus Michael CM

Chemistry (Weinheim an der Bergstrasse, Germany) 20210125 10

Due to its unique magnetic properties offered by the open-shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state ...[more]

PMID: 33264485

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Project description:BackgroundWe previously investigated methods for separating mutagenic contaminants from aqueous solutions using cellulose-bearing covalently bound trisulfo-Cu-phthalocyanine (blue cotton and blue rayon). Mutagenic contaminants with three or more fused aromatic rings in their structures were adsorbed onto blue cotton and rayon. Since Cu-phthalocyanine is considered an unsuitable absorption ligand for byproducts of water chlorination, such as 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (Mutagen X or MX), we investigated the development of a new material for the elimination of MX from aqueous solvents.ResultsWe selected green cellulose powder bearing ferrous phthalocyanine (FePh), hereafter referred to as green cellulose or GP, as the candidate material. GP is composed of cationized cellulose (white cellulose, WP) and FePh tetracarboxylic acid. The mutagenicity of MX dissolved in buffer or dimethyl sulfoxide (DMSO) solution significantly decreased after treatment with GP. The effects of GP on the elimination of MX from the solvent were very close to being expired after 70 cycles of repeated adsorption of the same GP, and the capacity of GP for MX removal was estimated to be exhausted after 120 cycles of repeated adsorption based on the extrapolation of the obtained result; thus, the interacting ligands on GP may be saturated after complete MX adsorption. The mutagenicity of MX dissolved in aqueous buffer significantly decreased after treatment at pH7.4 but not at pH 4.0. Since MX is dissociated to be the anionic form at pH 6 or higher, the negative charge of MX in the buffer at pH 7.4 may interact with the positive charge of ferrous ions in GP to create a linkage between MX and GP. After GP adsorbed MX, mutagenicity was extracted with water or acetonitrile and recovered in the eluent. Thus, the reversible interaction between MX and FePh may have caused adsorption of MX onto GP.ConclusionGP could be used as a new eliminator and recovery agent for MX in chlorinated drinking water. Developing new materials for the removal and recovery of agents for the detection of mutagenic contaminant-related chlorination in water is beneficial for environmental health.

Project description:Octacyano-metal-phthalocyanine MPc(CN)8 is a promising n-type stable organic semiconductor material with eight cyano groups, including a strong electron-withdrawing group at its molecular terminals. However, a thorough investigation of MPc(CN)8 has not yet been conducted. Therefore, we synthesized FePc(CN)8 and investigated its crystal structure, chemical and electronic states, electrical properties, photocatalytic activity, and magnetic properties. In this paper, we discuss the various properties of MPc(CN)8 in comparison with those of FePc. X-ray diffraction measurements indicated that the crystal structure of FePc(CN)8 was strongly influenced by the cyano groups and differed from the α- and β-forms of FePc. The space group P4/mcc structure of FePc(CN)8 was similar to that of the x-form of LiPc. The ultraviolet-visible (UV-vis) absorption spectrum of FePc(CN)8 was observed at wavelengths longer than that of FePc. Density functional theory-based molecular orbital calculations indicated that the energy gap of FePc(CN)8 is smaller than that of FePc, which can lead to the observation of the Q-band in the UV-vis absorption spectrum of FePc(CN)8 at longer wavelengths than that of FePc. Because FePc(CN)8 has a wider optical absorption band in the visible region than FePc, its photocatalytic activity is approximately four times higher than that of FePc. The conductivity of FePc(CN)8 was also higher than that of FePc, which is due to the larger overlap of π-electron clouds of the molecules in the crystal structure of FePc(CN)8. Magnetic measurements revealed that FePc(CN)8 exists in an antiferromagnetic ground state. The magnetic properties of FePc(CN)8 are specific to its crystal structure, with direct exchange interactions between Fe2+ ions and π-electron-mediated interactions. In particular, the Pauli paramagnetic behavior at high temperatures and the antiferromagnetic behavior at low temperatures (Weiss temperature θ = -4.3 ± 0.1 K) are characteristic of the π-d system.

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Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO₂ Exposure.

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Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO<sub>2</sub> Exposure.

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Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO2 Exposure.

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Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO<sub>2</sub> Exposure.

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Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO₂ Exposure.