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Structural Versatility and Supramolecular Isomerism in Redox‐Active Tetra‐ and Hexaruthenium Macrocycles
Author(s) -
Fink Daniel,
Orth Nicole,
Linseis Michael,
IvanovićBurmazović Ivana,
Winter Rainer F.
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000387
Subject(s) - chemistry , tetra , cyclic voltammetry , supramolecular chemistry , electron paramagnetic resonance , redox , thiophene , spectroscopy , crystallography , nuclear magnetic resonance spectroscopy , electrochemistry , furan , stereochemistry , organic chemistry , medicinal chemistry , crystal structure , nuclear magnetic resonance , electrode , physics , quantum mechanics
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 .