Application of a planar superatom model on [Hg(5)(C(CF(3))(2))]. Bonding and magnetic response considerations into a...

Application of the planar superatom model to describe the electronic structure, and to gain insights into the stabilization of metal macrocycles supporting closed-shell d(10)-d(10) interactions, is studied through analysis of the membered ring composed by Hg(ii) atoms, namely, [Hg(C(CF3)2)]5. Its electronic structure resembles the level sequence given for a planar jellium model, revealing an electronic configuration given by 1s(2) 1p(4)x,y 1d(4)xy,x(2)-y(2). The analysis of the population of each level of the Hg5core, denotes a slight net bonding into the [Hg(C(CF3)2)]5 ring. However, stabilization is mainly supported by the balance given by a similar population of the jellium levels, which is suggested to be a different scheme for stabilizing d(10) macrocyclic clusters with metallophilic interactions, in the category of long d(10)-d(10) contacts. The extension of the planar jellium model to the relativistic case, including spin-orbit coupling considering the D5h* point group, denotes the consequent splitting for levels with l ≠ 0, namely, 1px,y and 1dxy,x(2)-y(2). In this framework, the electronic configuration is given by 1s1/2(2) 1p3/2(2) 1p1/2(2) 1d5/2(2) 1d3/2(2), which contribute to the analysis of the electronic structure of planar clusters in terms of spin-orbit coupling, involving molecular spinors (j = l ± s) instead of molecular orbitals (pure l).