Dithia[3.3]paracyclophane-bridged bimetallic ruthenium acetylide complexes: synthesis, structures and influence of transannular π–π interactions on their electronic properties

Two dithia[3.3]paracyclophane-bridged bimetallic ruthenium acetylide complexes 2 and 3, in which the upper deck of the cyclophanes were assembled with naphthalenyl and anthracenyl rings, have been designed and synthesized. X-ray crystal structures of 2 and 3 show that there are effective transannular π–π interactions between the two rings in the cyclophane unit. Electrochemistry studies revealed that the successive introduction of naphthalenyl and anthracenyl rings reduced the thermodynamic stability of the corresponding mixed-valence states of 2 and 3. Radical cations and dications of complexes 2 and 3 were generated after the addition of 1.0 or 2.0 equivalents of ferrocenium hexafluorophosphate ([FcH][PF6]). The ν(CC) of radicals 2+++ and 3++ shift 86 nm and 88 nm in contrast to 2 and 3, respectively. UV-Vis-NIR spectra of 2+++ and 3++ exhibited three enveloped transitions in the NIR (10 000–4000 cm−1) range. DFT studies showed that the compositions of the FMOs of 2 and 3 are more naphthalenyl and anthracenyl in character than the upper deck of complex 1. Spectroscopy and DFT studies indicated that the influence of transannular π–π interactions on the electronic transitions is more pronounced than in complex 1.