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Constitutional Isomers of Macrocyclic Tetraruthenium Complexes with Vastly Different Spectroscopic and Electrochemical Properties

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2018

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https://doi.org/10.1021/acs.organomet.8b00057
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Organometallics. 2018, 37(12), pp. 1817-1820. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/acs.organomet.8b00057

Zusammenfassung

Two constitutionally isomeric tetraruthenium macrocycles were constructed from either symmetrically (2-S) or unsymmetrically (2-A) functionalized thiophene-based building blocks. Both compounds were fully characterized by NMR spectroscopy and high-resolution ESI MS. Despite their identical composition and close structural resemblance, the two isomers exhibit vastly different electrochemical and spectroscopic properties as a consequence of the different extensions of their π-conjugated subunits. In particular, mixed-valent 2-A+/2+/3+ absorb weakly in the near infrared as a consequence of electronic through-bond coupling between neighboring oxidized and reduced sites, whereas 2-S+/2+/3+ do not.

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ISO 690FINK, Daniel, Michael LINSEIS, Rainer F. WINTER, 2018. Constitutional Isomers of Macrocyclic Tetraruthenium Complexes with Vastly Different Spectroscopic and Electrochemical Properties. In: Organometallics. 2018, 37(12), pp. 1817-1820. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/acs.organomet.8b00057
BibTex
@article{Fink2018-06-25Const-42691,
  year={2018},
  doi={10.1021/acs.organomet.8b00057},
  title={Constitutional Isomers of Macrocyclic Tetraruthenium Complexes with Vastly Different Spectroscopic and Electrochemical Properties},
  number={12},
  volume={37},
  issn={0276-7333},
  journal={Organometallics},
  pages={1817--1820},
  author={Fink, Daniel and Linseis, Michael and Winter, Rainer F.}
}
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    <dcterms:abstract xml:lang="eng">Two constitutionally isomeric tetraruthenium macrocycles were constructed from either symmetrically (2-S) or unsymmetrically (2-A) functionalized thiophene-based building blocks. Both compounds were fully characterized by NMR spectroscopy and high-resolution ESI MS. Despite their identical composition and close structural resemblance, the two isomers exhibit vastly different electrochemical and spectroscopic properties as a consequence of the different extensions of their π-conjugated subunits. In particular, mixed-valent 2-A&lt;sup&gt;+/2+/3+&lt;/sup&gt; absorb weakly in the near infrared as a consequence of electronic through-bond coupling between neighboring oxidized and reduced sites, whereas 2-S&lt;sup&gt;+/2+/3+&lt;/sup&gt; do not.</dcterms:abstract>
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