Structural Versatility and Supramolecular Isomerism in Redox-Active Tetra- and Hexaruthenium Macrocycles

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2020
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Orth, Nicole
Ivanovic-Burmazovic, Ivana
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European Journal of Inorganic Chemistry. Wiley. 2020, 2020(29), pp. 2816-2829. ISSN 1434-2421. eISSN 1434-1948. Available under: doi: 10.1002/ejic.202000387
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We report on six macrocyclic tetra‐ and hexaruthenium complexes formed by the self‐assembly of 2,5‐divinylthiophene‐ or 2,5‑divinylfuran‐bridged diruthenium and 2,5‐thiophene‐, ‐furan‐ or ‑pyrroledicarboxylate linkers. All complexes were scrutinized by NMR spectroscopy and UHR ESI‐MS, cyclic and square wave voltammetry and, in five cases, by X‐ray diffraction analyses. Although the utilized building blocks differ only slightly with respect to their intrinsic bite angles, the resulting macrocycles exhibit remarkable structural versatility. Electrolysis inside an optically transparent electrochemical (OTTLE) cell provided their associated di‐/tri‐ and tetra‐/hexacations, which were studied by IR, UV/Vis/NIR and EPR spectroscopy. The divinylthiophene‐furandicarboxylate complex 2‑TF provides a rare example of supramolecular isomerism in metallamacrocyclic complexes. Thus, hexanuclear 2‑TF 6 is initially formed as a kinetic isomer, which subsequently transforms slowly and cleanly into tetranuclear 2‑TF 4 .

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ISO 690FINK, Daniel, Nicole ORTH, Michael LINSEIS, Ivana IVANOVIC-BURMAZOVIC, Rainer F. WINTER, 2020. Structural Versatility and Supramolecular Isomerism in Redox-Active Tetra- and Hexaruthenium Macrocycles. In: European Journal of Inorganic Chemistry. Wiley. 2020, 2020(29), pp. 2816-2829. ISSN 1434-2421. eISSN 1434-1948. Available under: doi: 10.1002/ejic.202000387
BibTex
@article{Fink2020-08-09Struc-49401,
  year={2020},
  doi={10.1002/ejic.202000387},
  title={Structural Versatility and Supramolecular Isomerism in Redox-Active Tetra- and Hexaruthenium Macrocycles},
  number={29},
  volume={2020},
  issn={1434-2421},
  journal={European Journal of Inorganic Chemistry},
  pages={2816--2829},
  author={Fink, Daniel and Orth, Nicole and Linseis, Michael and Ivanovic-Burmazovic, Ivana and Winter, Rainer F.}
}
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