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Issue 7, 2018
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Redox-active diaminoazobenzene complexes of rhodium(III): synthesis, structure and spectroscopic characterization

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Abstract

Herein, the reactivity of an aromatic diamine, 2,2′-diaminoazobenzene 1 [H2NLNH2], with rhodium salts was investigated. Diverse coordinations, specifically single and double NH deprotonated forms, of the title ligand are obtained during metallation, affording mononuclear 2 and dinuclear 3 complexes, respectively. An unprecedented edge-shared bioctahedral geometry with a syn configuration (sterically encumbered) about the RhIII2N2 core is obtained with pincer-type NNN ligation. Both complexes are redox-active and provide well-defined oxidative responses, and the reversibility of the redox-couples is enhanced with the decreasing temperature. The spectroscopic study indicates the formation of open-shell species derived from the precursor amido complexes, and these species are believed to be ligand-centered π radicals. The incorporation of both electron-poor azo and electron-rich amido moieties imparts the possibility of low-energy electronic transitions within the tridentate ligand (the push–pull effect). Furthermore, the occurrence of ILCT has been substantiated theoretically (TDDFT and NTO).

Graphical abstract: Redox-active diaminoazobenzene complexes of rhodium(iii): synthesis, structure and spectroscopic characterization

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The article was received on 05 Dec 2017, accepted on 25 Feb 2018 and first published on 28 Feb 2018


Article type: Paper
DOI: 10.1039/C7NJ04790H
Citation: New J. Chem., 2018,42, 5548-5555
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    Redox-active diaminoazobenzene complexes of rhodium(III): synthesis, structure and spectroscopic characterization

    S. Roy, S. Pramanik, T. Ghorui, S. Dinda, S. C. Patra and K. Pramanik, New J. Chem., 2018, 42, 5548
    DOI: 10.1039/C7NJ04790H

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