title: How much tetraradical character is present in the Si₆Ge₉ cluster?
abstract: This study discusses in detail the supposedly tetraradicaloid nature of a spirobis(pentagerma[1.1.1]propellane) derivative recently reported by Ito et al. (J. Am. Chem. Soc., 2013, 135, 6770). The electronic structure properties of the Si6Ge9 cluster are computationally explored by means of the composition of the ground state wavefunction, excitation energies to low-lying singlet, triplet and quintet states, and magnetic couplings between radical centers. Two main conclusions can be extracted from the obtained results regarding the radical character of spriobis(pentagerma[1.1.1]propellane): (i) the ground state of the Si6Ge9 cluster presents a rather small amount of effective unpaired electrons, which might be related to its chemical stability and (ii) there is in fact a perceptible tetraradical character within the small overall radical nature of the molecule. The proposed description do not contradict the conclusions drawn by the introductory work of Ito et al., but it provides a more detailed and precise interpretation of radical character of the molecule.
authors.affiliation: Faculty of Chemistry, Donostia International Physics Center (DIPC), University of the Basque Country (UPV/EHU), P.K. 1072, 20080 Donostia, Spain, and IKERBASQUE, Basque Foundation for Science, 48011, Bilbao, Spain.
authors.forename: David
authors.initials: D
authors.lastname: Casanova
keywords: electronic structure; excited states; magnetic coupling; spin-flip; tetraradical character