MIM-based MOFs have a promising future in the preparation of smart materials. The vast number of structural possibilities which offer their design are disclosed in this review.

Despite their high degree of flexibility, tribenzylamine molecules endowed with one ureido group in every arm are avid self-assemblers with a high capacity for self-recognition. Narcissistic self-sorting or chiral self-discrimination events take place when two modules associate giving capsular aggregates. The size of the cavity may be modulated by the relative position of the ureido group and the amino function works as a pH switch of the rupture–reassembly process. When chiral racemic triureas are present the self-assembly is highly diastereoselective.

The synthesis of a set of benzylic amide [1]rotaxanes via a self-templating clipping approach is described. This methodology supposes the 1 + 1 coupling of isophthaloyl dichloride with an acyclic diamine precursor incorporating a templating arm. The structure of the threaded compounds was determined both in solution and in the solid state. The conversion into the corresponding unthreaded isomers, also obtained by deslipping of [2]rotaxane models, was evaluated in competitive and non-competitive hydrogen-bonding solvents. The switch of the extended and contracted lasso-like isomers of a bistable [1]rotaxane by an olefin isomerization promoted by UV light irradiation was also accomplished and their ring positional integrity was examined.

A detailed mechanistic study of the diastereoselective CsOH-promoted cyclization of interlocked fumaramides to give β-lactams is described. The mechanistic analysis comprises the experimental evaluation of the structure-reactivity relationship for a wide range of fumaramides [2]rotaxanes (Hammet-plots), KIE studies with deuterium-labelled interlocked fumaramides and computational analysis of two alternative mechanistic pathways for the cyclization process. The obtained results confirm that: (a) the rate-determining step is the deprotonation of the N-benzyl group of the thread by the amidate group of the macrocycle generated by the external base, (b) the polyamide macrocycle plays an important role not only as activating element but also as the stereodifferenciating factor responsible for the observed diastereoselection and (c) the higher flexibility of the adamantyl core speeds up the cyclization process in diadamantyl-derived rotaxanes.

The synthesis of a series of interlocked profragrances and the study of the controlled release of the corresponding scents are reported. The structures of the profragrances are based on a [2]pseudorotaxane scaffold with a fumaramate thread derived from perfumery alcohols and a tetrabenzylamido ring. The delivery of the scents was accomplished by sequential thermal dethreading and further enzymatic hydrolysis. Alternatively, the dethreading can be achieved by increasing the polarity of the solvent or photochemical isomerization. The temperature of dethreading can be modulated by the steric demand of the ends of the thread, which allows the selection of different precursor structures depending on the desired rates of delivery. The inputs and outputs for the controlled release of the interlocked profragrances correspond to those of YES or AND logic gates.