A digold­(I) complex with a pyrene-di-N-heterocyclic carbene ligand has been obtained and fully characterized. The host–guest properties of the complex were studied in chloroform with a series of polycylic aromatic hydrocarbons (PAHs), and the association constants were determined. The affinity increases with the size of the PAH, with a maximum binding constant of 105 M–1 for the aggregation with coronene. The catalytic activity of the complex was tested in the hydroamination of phenylacetylene with three different amines. The studies showed that the addition of coronene to the reaction medium produces an enhancement of about 20–30% in the activity of the complex.

A series of platinum complexes with cis-oriented polyaromatic N-heterocyclic carbene ligands were prepared and characterized. The relative disposition of the polyaromatic ligands about the metal make these compounds to behave as a metallofolder, with a cavity defined by the void space between the polyaromatic functionalities. The complexes were used as receptors of organic molecules, where they showed selective affinity for binding electrondeficient aromatic substrates, such as 1,2,4,5-tetracyanobenzene (TCNB), 2,4,7-trinitro-9-fluorenone (TNFLU) and 1,4,5,8-naphtalenetetracarboxylic dianhydride (NTCDA). The binding affinities of two of the metallofolders with these substrates were determined by means of 1 H NMR titrations. Electrospay mass spectrometry (ESI-MS) was also used to assess the affinities. The molecular structure of one of the platinum folders was determined in the presence of TCNB, showing the clear interaction between this guest molecule and the folder formed by the two mutually cis polyaromatic ligands. This work demonstrates how the presence of the mutually cis polyaromatic ligands may constitute a very useful tool for the preparation of metal-based receptors.

Porous monolithic advanced functional materials based on supported ionic liquid-like phase (SILLP) systems were used for the preparation of oleophilic and hydrophobic cylindrical membranes and successfully tested as eco-friendly and safe systems for oil/water separation and for the continuous integration of catalytic and separation processes in an aqueous-organic biphasic reaction system.

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