Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 23, Issue 26, Pages 6380-6390Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201700137
Keywords
electrochemistry; EPR spectroscopy; photochemistry; radiolytic reduction; viologen
Categories
Funding
- European Research Council ERC-StG (PhotoSi) [278912]
- MIUR [FIRB RBAP11C58Y]
- European Research Council (ERC) [278912] Funding Source: European Research Council (ERC)
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A shape-persistent molecule, featuring four bipyridinium units, has been synthesized that upon reduction undergoes intermolecular pimerization because of the rigid architecture of the molecule. The pimerization process has been investigated by a variety of techniques, such as absorption measurements, EPR spectroscopy, as well as gamma and pulse radiolysis, and compared with the behavior of a model compound. Computational studies have also been performed to support the experimental data. The most interesting feature of the tetramer is that pimerization occurs only above a threshold concentration of monoreduced species, on the contrary to the model compound. Furthermore, there is an increase of the apparent pimerization constant by increasing the concentration of reduced bipyridinium units. These results have been interpreted by the fact that pimerization is favored in the tetrahedrally shaped molecule because of a cooperative mechanism. Each multiply reduced molecule can indeed undergo multiple intermolecular interactions that enhance the stabilization of the system, also leading to hierarchical supramolecular growth. The resulting supramolecular system formed by such intermolecular pimerization should exhibit a diamond-like structure, as suggested by a simplified modeling approach. The intermolecular nature of the pimerization process occurring in the tetramer has been demonstrated by measuring the corresponding bimolecular rate constant by pulsed radiolysis experiments.
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