Products Cited in Publications Worldwide Reversible Multielectron Release from Redox-Active Three-Dimensional Molecular Barrels with Ruthenium-Alkenyl Moieties

Reversible Multielectron Release from Redox-Active Three-Dimensional Molecular Barrels with Ruthenium-Alkenyl Moieties

Das, Rajorshi; Linseis, Michael; Scheerer, Stefan; Zoller, Katrin; Senft, Laura; Ivanovic-Burmazovic, Ivana; Winter, Rainer F.

DOI: PMID:

Abstract

Three-dimensional mol. barrels Ru6-4 and Ru6-5 were synthesized in high yields from dinuclear ruthenium-vinyl clamps and tritopic triphenylamine-derived carboxylate linkers and characterized by multinuclear NMR spectroscopy including 1H-1H COSY and 1H DOSY measurements, high-resolution electrospray ionization mass spectrometry, and X-ray crystallog. The metal frameworks of the cages adopt the shape of twisted trigonal prisms, and they crystallize as racemic mixtures of interdigitating Δ- and Λ-enantiomers with a tight columnar packing in Ru6-4. Electrochem. studies and redox titrations revealed that the cages are able to release up to 11 electrons on the voltammetric timescale and that their cage structures persist up to the hexacation level. IR and UV-vis-near-IR spectroelectrochem. studies confirm substituent-dependent intramol. electronic communication within the π-conjugated 1,3-divinylphenylene backbone in the tricationic states, where all three divinylphenylene-bridged diruthenium clamps are present in mixed-valent radical cation states. The formation of 1:3 charge-transfer salts with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane as the electron acceptor is also demonstrated.

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