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Localized mixed-valence and redox activity within a triazole-bridged dinucleating ligand upon coordination to palladium

Broere, D. L. J., Plessius, R., Tory, J., Demeshko, S., de Bruin, B., Siegler, M. A., Hartl, F. and van der Vlugt, J. I. (2016) Localized mixed-valence and redox activity within a triazole-bridged dinucleating ligand upon coordination to palladium. Chemistry- A European Journal, 22 (39). pp. 13965-13975. ISSN 1521-3765

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To link to this item DOI: 10.1002/chem.201601900

Abstract/Summary

The new dinucleating redox-active ligand (LH4), bearing two redox-active NNO-binding pockets linked by a 1,2,3-triazole unit, is synthetically readily accessible. Coordination to two equivalents of PdII resulted in the formation of paramagnetic (S=inline image ) dinuclear Pd complexes with a κ2-N,N′-bridging triazole and a single bridging chlorido or azido ligand. A combined spectroscopic, spectroelectrochemical, and computational study confirmed Robin–Day Class II mixed-valence within the redox-active ligand, with little influence of the secondary bridging anionic ligand. Intervalence charge transfer was observed between the two ligand binding pockets. Selective one-electron oxidation allowed for isolation of the corresponding cationic ligand-based diradical species. SQUID (super-conducting quantum interference device) measurements of these compounds revealed weak anti-ferromagnetic spin coupling between the two ligand-centered radicals and an overall singlet ground state in the solid state, which is supported by DFT calculations. The rigid and conjugated dinucleating redox-active ligand framework thus allows for efficient electronic communication between the two binding pockets.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:66561
Publisher:Wiley

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