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.
It is advisable to refer to the publisher's version if you intend to cite from this work. See Guidance on citing. To link to this item DOI: 10.1002/chem.201601900 Abstract/SummaryThe 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.
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