Publications 2019

The present paper reports on the formation and on the electrochemical/spectroscopic characterization of inclusion complexes formed in aqueous media between cucurbit[7 or 8]urils cavitands (CB[7], CB[8]) and a rigid four-pointed star-shaped viologen-appended porphyrin tecton. The formation of discrete 4:1 pseudo-rotaxane-like caviplexes, involving threading of CB[n] rings on the rigid viologen-based star's branches has been demonstrated by nuclear magnetic resonance and mass spectrometry measurements. Then, the photo- and redox-triggered formation of 2D supramolecular assemblies involving CB[8]s and the four electron reduced tectons as key building elements, has been established on the ground of in-depth electrochemical and spectroscopic analyses supported by quantum calculations. The CB[8]-promoted intermolecular π-dimerization of the viologen cation radicals introduced at the meso positions of the porphyrin plateform has been brought to light through the diagnostic signatures of the 1:2 host-guest ternary caviplexes formed between viologen and CB[8] and by spectroscopic data collected after electrochemical, chemical or photochemical reduction of the viologen-based tectons. The CB[8] hosts not only proved useful to promote the redox-triggered formation of supramolecular assemblies, it was also found to prevent the chemical reduction of the porphyrin ring in aqueous media and its subsequent conversion into phlorin products.

This review article focuses on supramolecular assemblies involving cucurbit[n]uril-based containers and viologen guests as key building elements. Cucurbit[n]urils (CB[n], n = 5–8,10) are fascinating hosts forming a wide range of inclusion complexes (caviplexes) with 4,4′-bipyridinium salts, known as viologens, either as discrete 1:1 inclusion compounds with CB[7] or as ternary inclusion compounds involving two hosts or two guests (2:1 with CB[7] and 1:2 or 1:1:1 with CB[8]). This property is currently being actively exploited to design and prepare self-assembled dynamic stimuli-responsive supramolecular polymers including gels, vesicles, films and organized arrays of polymeric microspheres or nanoparticles. This review highlights the main benefits of such polymers and gives an overview of the achievements and progress made in this field over the past decades. 

In this article, we present the synthesis of new cryptophane-type hosts capable of binding xenon in aqueous media and that may be useful for the development of xenon-based magnetic resonance imaging derivatives. The synthetic route proposed was chosen to facilitate both the introduction of water-solubilizing substituents and the functionalization of the host with a single arm showing recognition properties that constitute two crucial steps. This was made possible by preparing new cryptophane-223 derivatives bearing two different chemical functions that can be easily modified at a later stage. Thus, subsequent reactions allowed the design of a new cryptophane host able to bind zinc or nickel cations. The ability of this molecule to bind cationic species was assessed by calorimetric titration experiments and hyperpolarized 129Xe NMR. The advantages and disadvantages of this approach are discussed.