Organometallic boxes built from 5,10,15,20-tetra(4-pyridyl)porphyrin panels and hydroxyquinonato-bridged diruthenium clips

Self-assembly of 5,10,15,20-tetra(4-pyridyl)porphyrin (tpp-H₂) tetradentate panels with dinuclear arene ruthenium clips Ru₂(η⁶-arene)₂(dhbq)Cl₂] (arene = C₆H₅Me, p-PrⁱC₆H₄Me, C₆Me₆; dhbq = 2,5-dihydroxy-1,4-benzoquinonato) affords the cationic organometallic boxes Ru₈(η⁶-C₆H₅Me)₈(tpp-H₂)₂(dhbq)₄]⁸⁺ (1]⁸⁺), Ru₈(η⁶-p-PrⁱC₆H₄Me)₈(tpp-H₂)₂(dhbq)₄]⁸⁺ (2]⁸⁺) and Ru₈(η⁶-C₆Me₆)₈(tpp-H₂)₂(dhbq)₄]⁸⁺ (3]⁸⁺). These octanuclear cations have been isolated as their triflate salts and characterised by mass spectrometry, NMR and IR spectroscopy. The molecular structure of these systems was deduced by one-dimensional and two-dimensional NMR experiments (ROESY, COSY, HSQC).