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Charge transfer complexes of lanthanide 3,5-dinitrobenzoates and 1,2-phenylenediamine

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Abstract Crystallization of lanthanide 3,5-dinitrobenzoates from MeCN-DMSO media in the presence of o-phenylenediamine (PDA) brings about the complexes of two types, the binuclear complexes built of the single molecules [Ln2(O2CC6H3(NO2)2)6(PDA)2(DMSO)2]… Click to show full abstract

Abstract Crystallization of lanthanide 3,5-dinitrobenzoates from MeCN-DMSO media in the presence of o-phenylenediamine (PDA) brings about the complexes of two types, the binuclear complexes built of the single molecules [Ln2(O2CC6H3(NO2)2)6(PDA)2(DMSO)2] and the supramolecular polymers [Ln2(O2CC6H3(NO2)2)6DMSO4]·PDA·4MeCN. In both types of complexes, charge transfer (CT) between PDA molecules and 3,5-dinitrobenzoate fragments takes place; in the first case it is intramolecular, in the second case the binuclear fragments are united into supramolecular chains due to CT effect. Compounds of different types are often formed simultaneously; the complexes of the first type were isolated in pure form and studied for Gd, Tb, and Ho, while the complexes of the second type were obtained for Dy and Er. The charge transfer in the complexes was characterized by reflectance spectra; according to EPR study, it is too weak to make any paramagnetic contribution.

Keywords: transfer complexes; lanthanide dinitrobenzoates; charge; complexes lanthanide; charge transfer

Journal Title: Journal of Molecular Structure
Year Published: 2020

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