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Updated: Sep 2, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Reversible Multielectron Release from Redox-Active Three-Dimensional Molecular Barrels with Ruthenium-Alkenyl
Rajorshi Das1, Michael Linseis1, Stefan Scheerer1
1Fachbereich Chemie, Universität Konstanz, Universitätsstraße 10, 78457 Konstanz, Germany.
Abstract:
Three-dimensional molecular barrels Ru-4 and Ru-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 crystallography. 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 Ru-4. Electrochemical 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-infrared spectroelectrochemical studies confirm substituent-dependent intramolecular 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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