Dynamic combinatorial chemistry.

The state of the art in the mechanisms operating in imine chemistry in organic solvents is critically discussed in the present review. In particular, the reaction pathways involved in imine formation, transimination and imine metathesis in organic media are taken into account, with the aim of organizing the poor, and sometimes scattered, information available in the literature. It is shown that 4-membered cyclic transition states, either polar or apolar, can be considered a leitmotif for the chemistry of imines in organic solvents. However, it is pointed out that further investigations will be necessary to reach an adequate degree of knowledge of the mechanisms involved in such important reversible processes.

Mechanisms of imine exchange reactions in organic solvents

The formation and exchange processes of imines of salicylaldehyde, pyridine-2-carboxaldehyde, and benzaldehyde have been studied, showing that the former has features of particular interest for dynamic covalent chemistry, displaying high efficiency and fast rates. The monoimines formed with aliphatic α,ω-diamines display an internal exchange process of self-transimination type, inducing a local motion of either “stepping-in-place” or “single-step” type by bond interchange, whose rate decreases rapidly with the distance of the terminal amino groups. Control of the speed of the process over a wide range may be achieved by substituents, solvent composition, and temperature. These monoimines also undergo intermolecular exchange, thus merging motional and constitutional covalent behavior within the same molecule. With polyamines, the monoimines formed execute internal motions that have been characterized by extensive one-dimensional, two-dimensional, and EXSY proton NMR studies. In particular, with linear poly...

Merging Constitutional and Motional Covalent Dynamics in Reversible Imine Formation and Exchange Processes

The interaction of an external effector, ZnII ions, with a constitutional dynamic library of fluorescent polyiminofluorenes leads to component exchange, which generates an entity responding by a change in emission to the effector that has induced its formation. The overall coupled system displays a tuning of optical signal, resulting from two synergistic processes:  adaptative constitutional reorganization and self-sensing. In broader terms, this work highlights the perspectives opened by constitutional dynamic chemistry toward the design of smart materials, capable of expressing different latent properties in response to environmental conditions.

Constitutional Dynamic Self-Sensing in a ZincII/Polyiminofluorenes System

A nanostructured poly(acylhydrazone), which is reversibly formed in acidic aqueous solution from di(aldehyde) and di(acylhydrazine) monomers with appended hexaglyme groups, was found to display lower critical solution (LCS) behavior. Remarkably, under acidic conditions in which polymerization is reversible, large and reversible molecular weight (Mw) increases were observed in response to elevated temperatures, both below and above the LCS temperature. No variation in Mw was evident under neutral and alkaline conditions, in which the acylhydrazone condensation is essentially irreversible. Results of turbidometry studies, size-exclusion chromatography–multiangle laser light scattering (SEC–MALLS), and transmission electron microscopy (TEM) suggest that heating the polymer below the LCS temperature leads to polymer growth with preservation of the characteristic nanostructured morphology, whereas the onset of the microphase separated state causes a fundamental change in morphology, in which the polymer chains...

D. L. Leussing

Papers

Stabilities, rates of formation, and rates of transimination in aqueous solutions of some zinc(II)-Schiff base complexes derived from salicylaldehyde