Abstract
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‐TF6 is initially formed as a kinetic isomer, which subsequently transforms slowly and cleanly into tetranuclear 2‐TF4.
Highlights
Metallamacrocycles represent a fascinating class of cyclic molecules of intrinsic beauty due to their inherently high symmetry
All new macrocyclic complexes were obtained following a general synthesis route, which has so far allowed for the construction of cyclic structures from divinylphenylene-bridged diruthenium building blocks
Hexanuclear macrocycle 2-TF6 is the noteworthy exception and undergoes slow isomerization to its tetranuclear supramolecular isomer 2-TF4.[24]. The purities of all new metallamacrocycles were confirmed by NMR spectroscopy
Summary
Metallamacrocycles represent a fascinating class of cyclic molecules of intrinsic beauty due to their inherently high symmetry. As the three tetranuclear macrocyclic structures originating from parent complex 1-T differ only in the dicarboxylate linker, their molecular structures resemble each other closely (see Figure 4 and Table 2).
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