Unique Type of BF2‐Capped Tetraoxobenzene π‐Complexes of “Cp*M”: Novel Organometallic Backbones for the Self‐Assembly of Porous Networks

Abstract

AbstractThe synthesis of two novel organometallic π complexes of a BF2‐capped tetraoxobenzene (TOB) of the general formulae [Cp*M‐η6‐{BF2‐TOB‐BF2}] (M = Ir, 2a; M = Rh, 2b) is reported together with their molecular structures ascertained by single‐crystal X‐ray diffraction studies. Complexes 2a and 2b are isostructural and show the formation of 3D porous supramolecular networks. Interestingly the supramolecular networks arise from the zwitterionic nature of 2a and 2b. Indeed, the individual molecules self‐assemble through the teamwork of dipolar H···F hydrogen and C···F halogen bonds, which leads to the formation of 3D networks with empty channels. These complexes hold promise for the design of a new class of porous materials with useful properties.