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Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities

Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities

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ANDERS, Patrick, Mario Robin RAPP, Michael LINSEIS, Rainer F. WINTER, 2018. Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities. In: Inorganics. 6(3), 73. eISSN 2304-6740. Available under: doi: 10.3390/inorganics6030073

@article{Anders2018-09Tetra-44407, title={Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities}, year={2018}, doi={10.3390/inorganics6030073}, number={3}, volume={6}, journal={Inorganics}, author={Anders, Patrick and Rapp, Mario Robin and Linseis, Michael and Winter, Rainer F.}, note={Article Number: 73} }

Linseis, Michael Anders, Patrick 2018-09 Winter, Rainer F. Rapp, Mario Robin Anders, Patrick Rapp, Mario Robin Linseis, Michael 2018-12-21T12:36:17Z Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities 2018-12-21T12:36:17Z eng Winter, Rainer F. Attribution 4.0 International 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<sup>−1</sup>·cm<sup>−1</sup>. 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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