Remarkable Magnetic Coupling Interactions in Multi-Beryllium-Expanded Small Graphene-like Molecules with Well-Defined Polyradical Characters

2017-04-03T14:19:40Z (GMT) by Meiyu Song Xinyu Song Yuxiang Bu
Multi-beryllium-expanded small graphene-like molecules including oligoacenes (mBe-nA) and graphene patches (mBe-GP) are computationally designed through introducing two or three Be atoms into the specific benzenoid rings of the graphene-like molecules, leading to replacement of some C–C bonds by the C–Be–C linkages with elongated C···C distances of about 3.3 Å in them. As a result, the elongation of the C···C bonds and insertion of more Be atoms make the two radical moieties in each molecule relatively separated and their interaction relatively weak. Both density functional theory and CASSCF calculations indicate that all these multi-Be-expanded graphene-like molecules exhibit well-defined polyradical characters: an open-shell singlet diradical for all mBe-nA and an open-shell singlet diradical or quintet tetraradical for mBe-GP depending on the Be-insertion patterns of the patches. The main findings in this work are that (i) a switching from the parent graphene-like closed-shell molecules (e.g., linear oligoacenes and graphene patches) to the open-shell singlet (diradical) or quintet (tetraradical) ground states can be realized by introducing Be as linkers into the graphene-like molecules; (ii) more importantly, the spin-coupling interactions of such mBe-nA and mBe-GP are remarkably large; and (iii) in these Be-modified molecules the Be–C bonds exhibit considerable covalent character and the Be···Be distances are 2.67–2.84 Å, implying weak Be­(s2)···Be­(s2) metallophilic interaction. This work would open a new perspective for the rational design of perfect and stable singlet diradicals or polyradicals with large spin-coupling constants on the basis of small closed-shell graphene-like molecules by multimetal incorporation and also encourage experimentalists to pursue and realize these interesting structures with enhanced magnetic properties in the future.