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Synthesis, characterization, and POM-protein interactions of a Fe-substituted Krebs-type Sandwich-tungstoantimonate.

ABSTRACT:

Abstract

The novel iron-substituted Krebs-type polyoxotungstate (C₁₂N₄H₁₁)₄Na₂H₅[(Fe(H₂O)₃)₂((FeO₂)_0.5(WO₂)_0.5)₂(?-SbW₉O₃₃)₂] (Fe-1) has been synthesized using ortho-phenylenediamine (opda) as a precursor for the in situ formation of the counter cation 2,3-diaminophenazinium (C₁₂N₄H₁₁)⁺ (2,3-DAP). Fe-1 has been thoroughly characterized in the solid state by single-crystal X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), IR spectroscopy, and elemental analysis as well as in solution by UV-Vis spectroscopy. The crystal structure of Fe-1 reveals ?-?-interactions between the aromatic systems of the unconventional 2,3-DAP counter cation. POM-protein interaction studies using SDS-PAGE revealed a non-proteolytic behavior of Fe-1 towards Human Serum Albumin (HSA) as a model protein.

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SUBMITTER: Tanuhadi E

PROVIDER: S-EPMC6533222 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature

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Synthesis, characterization, and POM-protein interactions of a Fe-substituted Krebs-type Sandwich-tungstoantimonate.

Tanuhadi Elias E Kampatsikas Ioannis I Giester Gerald G Rompel Annette A

Monatshefte fur chemie 20190429 5

<h4>Abstract</h4>The novel iron-substituted Krebs-type polyoxotungstate (C12N4H11)4Na2H5[(Fe(H2O)3)2((FeO2)0.5(WO2)0.5)2(β-SbW9O33)2] (Fe-1) has been synthesized using ortho-phenylenediamine (opda) as a precursor for the in situ formation of the counter cation 2,3-diaminophenazinium (C12 ...[more]

PMID: 31178605

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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.

Dataset Information

Synthesis, characterization, and POM-protein interactions of a Fe-substituted Krebs-type Sandwich-tungstoantimonate.

Abstract

Graphical abstract

Publications

Synthesis, characterization, and POM-protein interactions of a Fe-substituted Krebs-type Sandwich-tungstoantimonate.

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