Abstract
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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