Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities

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Inorganics. 2018, 6(3), 73. eISSN 2304-6740. Available under: doi: 10.3390/inorganics6030073
Zusammenfassung

We present four new tetraruthenium macrocycles built from two 1,4-divinylphenylene diruthenium and two isophthalic acid building blocks with peripheral, potentially mono- or tridentate donor functions attached to the isophthalic linkers. These macrocycles are characterized by multinuclear NMR spectroscopy, mass spectrometry and, in the case of the thioacetyl-appended complex 4, by X-ray crystallography. Cyclic and square wave voltammetry establish that the macrocycles can be oxidized in four consecutive redox steps that come as two pairs of two closely spaced one-electron waves. Spectroscopic changes observed during IR and UV/Vis/NIR spectroelectrochemical experiments (NIR = near infrared) show that the isophthalate linkers insulate the electroactive divinylphenylene diruthenium moieties against each other. The macrocycles exhibit nevertheless pronounced polyelectrochromism with highly intense absorptions in the Vis (2+/4+ states) and the NIR (2+ states) with extinction coefficients of up to >100,000 M−1·cm−1. The strong absorptivity enhancement with respect to the individual divinylphenylene diruthenium building blocks is attributed to conformational restrictions imposed by the macrocycle backbone. Moreover, the di- and tetracations of these macrocycles are paramagnetic as revealed by EPR spectroscopy.

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540 Chemie
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ruthenium; metallamacrocycle; electrochemistry; spectroelectrochemistry
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ISO 690ANDERS, Patrick, Mario Robin RAPP, Michael LINSEIS, Rainer F. WINTER, 2018. Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities. In: Inorganics. 2018, 6(3), 73. eISSN 2304-6740. Available under: doi: 10.3390/inorganics6030073
BibTex
@article{Anders2018-09Tetra-44407,
  year={2018},
  doi={10.3390/inorganics6030073},
  title={Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities},
  number={3},
  volume={6},
  journal={Inorganics},
  author={Anders, Patrick and Rapp, Mario Robin and Linseis, Michael and Winter, Rainer F.},
  note={Article Number: 73}
}
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    <dcterms:abstract xml:lang="eng">We present four new tetraruthenium macrocycles built from two 1,4-divinylphenylene diruthenium and two isophthalic acid building blocks with peripheral, potentially mono- or tridentate donor functions attached to the isophthalic linkers. These macrocycles are characterized by multinuclear NMR spectroscopy, mass spectrometry and, in the case of the thioacetyl-appended complex 4, by X-ray crystallography. Cyclic and square wave voltammetry establish that the macrocycles can be oxidized in four consecutive redox steps that come as two pairs of two closely spaced one-electron waves. Spectroscopic changes observed during IR and UV/Vis/NIR spectroelectrochemical experiments (NIR = near infrared) show that the isophthalate linkers insulate the electroactive divinylphenylene diruthenium moieties against each other. The macrocycles exhibit nevertheless pronounced polyelectrochromism with highly intense absorptions in the Vis (2+/4+ states) and the NIR (2+ states) with extinction coefficients of up to &gt;100,000 M&lt;sup&gt;−1&lt;/sup&gt;·cm&lt;sup&gt;−1&lt;/sup&gt;. The strong absorptivity enhancement with respect to the individual divinylphenylene diruthenium building blocks is attributed to conformational restrictions imposed by the macrocycle backbone. Moreover, the di- and tetracations of these macrocycles are paramagnetic as revealed by EPR spectroscopy.</dcterms:abstract>
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