N-Heterocyclic Carbenes: A Door Open to Supramolecular Organometallic Chemistry.

The field of metallosupramolecular chemistry is clearly dominated by the use of O-, N-, and P-donor Werner-type polydentate ligands. These molecular architectures are of high interest because of their wide range of applications, which include molecular encapsulation, stabilization of reactive species, supramolecular catalysis, and drug delivery, among others. Only recently, organometallic ligands have allowed the preparation of a variety of supramolecular coordination complexes, and the term supramolecular organometallic complexes (SOCs) is gaining space within the field of metallosupramolecular chemistry. While the early examples of SOCs referred to supramolecular architectures mostly containing bisalkenyl, diphenyl, or bisalkynyl linkers, the development of SOCs during the past decade has been boosted by the parallel development of multidentate N-heterocyclic carbene (NHC) ligands. The first examples of NHC-based SOCs referred to supramolecular assemblies based on polydentate NHC ligands bound to group 11 metals. However, during the last 10 years, several planar poly-NHC ligands containing extended π-conjugated systems have facilitated the formation of a large variety of architectures in which the supramolecular assemblies can contain metals other than Cu, Ag, and Au. Such ligands are Janus di-NHCs and trigonal-planar tris-NHCs-most of them prepared by our research group-which have allowed the preparation of a vast range of NHC-based metallosupramolecular compounds with interesting host-guest chemistry properties. Although the number of SOCs has increased in the past few years, their use for host-guest chemistry purposes is still in its earliest infancy. In this Account, we describe the achievements that we have made during the last 4 years toward broadening the applications of planar extended π-conjugated NHC ligands for the preparation of organometallic-based supramolecular structures, including their use as hosts for some selected organic and inorganic guests, together with the catalytic properties displayed by some selected host-guest inclusion complexes. Our contribution describes the design of several Ni-, Pd-, and Au-based metallorectangles and metalloprisms, which we used for the encapsulation of several organic substrates, such as polycyclic aromatic hydrocarbons (PAHs) and fullerenes. The large binding affinities found are ascribed to the incorporation of two cofacial panels with large π-conjugated systems, which provide the optimum conditions for guest recognition by π-π-stacking interactions. We also describe a series of digold(I) metallotweezers for the recognition of organic and inorganic substrates. These metallotweezers were used for the recognition of "naked" metal cations and polycyclic aromatic hydrocarbons. The recognition properties of these metallotweezers are highly dependent on the nature of the rigid connector and of the ancillary ligands that constitute the arms of the tweezer. A peculiar balance between the self-aggregation properties of the tweezer and its ability to encapsulate organic guests is observed.