Direct Synthesis of an Unprecedented Stable Radical of Nickel(II) 3,5-Bis(dimedonyl)azadiisoindomethene with Strong and Narrow Near-Infrared Absorption at λ ∼ 1000 nm

An unprecedented stable neutral radical nickel­(II) complex of 3,5-bis­(dimedonyl)­azadiisoindomethene (1) was prepared by the direct reaction between 1,3-diiminoisoindoline and dimedone. A new radical complex 1 has an intense and narrow absorption at 1008 nm and can be reduced to a less stable anio...

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Bibliographic Details
Published in:Inorganic chemistry 2017-06, Vol.56 (11), p.6052-6055
Main Authors: Makarova, Elena A, Zatsikha, Yuriy V, Newman, Kelly M. E, Paidi, Vinod K, Beletsky, Valeria A, van Lierop, Johan, Lukyanets, Evgeny A, Nemykin, Victor N
Format: Article
Language:English
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Summary:An unprecedented stable neutral radical nickel­(II) complex of 3,5-bis­(dimedonyl)­azadiisoindomethene (1) was prepared by the direct reaction between 1,3-diiminoisoindoline and dimedone. A new radical complex 1 has an intense and narrow absorption at 1008 nm and can be reduced to a less stable anionic [1]− with a typical aza­(dibenzo)­boron dipyrromethene (aza-BODIPY) UV−vis spectrum. Complex 1, along with two other colored condensation reaction products 2 and 3, was characterized by spectroscopy and X-ray crystallography, while the paramagnetic nature of 1 was probed by EPR and SQUID methods. Complex 1 forms dimers in the solid state with short (∼3.16 Å) Ni---Ni contacts. Redox data on 1 are indicative of a reversible reduction process in this complex; its magnetism suggests a S = 1/2 state with the spin density delocalized over the aza-BODIPY core. The experimental data 1 and [1]− were correlated with the density functional theory (DFT) and time-dependent DFT calculations.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.7b01140