A Multiresponsive Calix[6]arene Pseudorotaxane Empowered by Fluorophoric Dansyl Groups.

We report the synthesis and characterization, by means of NMR and UV-visible spectroscopy and electrochemical techniques, of a dansyl calix[6]arene derivative and of its pseudorotaxane complex with a bipyridinium-based axle. This novel macrocycle shows remarkable complexation ability, in analogy with parent compounds, while the dansyl moieties impart valuable features to the system. Indeed, these units: i) signal the state of the system by fluorescence; ii) can be reversibly protonated, enabling the modulation of the complexation abilities of the macrocycle; iii) participate in photoinduced electron transfer processes, which may be exploited to tune the stability of the supramolecular complex. Therefore, in this multiresponsive pseudorotaxane, the threading and de-threading motions of the molecular components can be modulated either by protonation of the calixarene host or by reduction of the bipyridinium guest, which can be accomplished both by electrochemical reduction and via photoinduced electron transfer. Overall, three orthogonal and reversible stimuli can be used to induce molecular movements of the pseudorotaxane components.

Calix[6]arene-Based [3]Rotaxanes as Prototypes for the Template Synthesis of Molecular Capsules.

In this work, the ability of several bis-viologen axles to thread a series of heteroditopic tris(N-phenylureido)calix[6]arene wheels to give interwoven supramolecular complexes to the [3]pseudorotaxane type was studied. The unidirectionality of the threading process inside these nonsymmetric wheels allows the formation of highly preorganised [3]pseudorotaxane and [3]rotaxane species in which the macrocycles phenylureido moieties, functionalised with either ester, carboxylic, or hydroxymethyl groups, are facing each other. As verified by NMR and semiempirical computational studies, these latter compounds possess the correct spatial arrangement of their subcomponents, which could lead, in principle, upon proper bridging reaction, to the realisation of upper-to-upper molecular capsules that are based on calix[6]arene derivatives.

Autonomous Non-Equilibrium Self-Assembly and Molecular Movements Powered by Electrical Energy.

The ability to exploit energy autonomously is one of the hallmarks of life. Mastering such processes in artificial nanosystems can open technological opportunities. In the last decades, light- and chemically driven autonomous systems have been developed in relation to conformational motion and self-assembly, mostly in relation to molecular motors. In contrast, despite electrical energy being an attractive energy source to power nanosystems, its autonomous harnessing has received little attention. Herein we consider an operation mode that allows the autonomous exploitation of electrical energy by a self-assembling system. Threading and dethreading motions of a pseudorotaxane take place autonomously in solution, powered by the current flowing between the electrodes of a scanning electrochemical microscope. The underlying autonomous energy ratchet mechanism drives the self-assembly steps away from equilibrium with a higher energy efficiency compared to other autonomous systems. The strategy is general and might be extended to other redox-driven systems.

Diametric calix[6]arene-based phosphine gold(I) cavitands.

We report the synthesis and characterization, in low polarity solvents, of a novel class of diametric phosphine gold(I) cavitands characterized by a 1,2,3-alternate geometry. Preliminary catalytic studies were performed on a model cycloisomerization of 1,6-enynes as a function of the relative orientation of the bonded gold(I) nuclei with respect to the macrocyclic cavity.

Merging Molecular Recognition and Gold(I) Catalysis with Triphoscalix[6]arene Ligands.

We report the synthesis and characterization of novel triphosphine calix[6]arene ligands. These supramolecular wheels, with recognition features governed by the hydrogen-bonding domain, were employed to synthesize multitasking trinuclear gold(I) complexes as a new platform for the synthesis of interwoven (pseudo)rotaxane species. In parallel, the multivalent, metal-bonded upper rim displayed catalytic features promoting highly selective gold-catalyzed cycloisomerization reactions of 1,6-enynes.

Heteroditopic Calix[6]arene Based Intervowen and Interlocked Molecular Devices.

Since the dawn of supramolecular chemistry, calixarenes have been employed as platforms onto which functional groups and binding sites can be loaded in a regio- and stereocontrolled manner for the recognition of charged and neutral species. Despite their wider annulus, potentially suitable to bind larger guests, the larger members of the calixarene series have been relatively less employed, mainly because of the synthetic difficulties to control their conformational flexibility and their regioselective functionalization. In this account, we will present the achievements gained during the last two decades on the use of the calix[6]arene as a platform to build-up structures in which the macrocycle acts as a wheel for the synthesis of oriented (pseudo)rotaxanes. We also account on how these calix[6]arene hosts affect the reactivity or spectroscopic properties of their bound guests.

Calix[6]arene-based Brønsted acids for molecular recognition and catalysis.

We report the synthesis of a versatile trifluoromethylsulfonamide calix[6]arene derivative with Brønsted acid features which can influence both molecular recognition and catalytic application. Indeed, in low polarity media, the trifluoromethyl-containing supramolecular wheel is able to respond to the complexation with charged species as a function of its selective ion-pair recognition. In parallel, the enhanced acidity is the key to promote Michael additions of indoles to nitroalkenes under pseudo-physiological reaction conditions (H2O, 37 °C).

Tuning the Fluorescence Through Reorientation of the Axle in Calix[6]arene-Based Pseudorotaxanes.

This work describes a calix[6]arene-based wheel that binds, in non-polar media, a stilbazolium salt to yield a mixture of pseudorotaxane orientational isomers. The isomer's abundance ratio evolves with time and can be reversibly tuned by adjusting the temperature. The spectroscopic properties, and notably the emission spectrum, of the bound guest depend on its orientation inside the non-palindromic wheel, suggesting such a system as a switch with spectroscopic readout.

Trisulfonamide calix[6]arene-catalysed Michael addition to nitroalkenes.

We describe the application of a novel family of trisulfonamide (TSA) calix[6]arenes in general acid catalysis. Hydrogen-bonding interactions between acidic TSA and methanol boosted the reactivity of the Michael addition of indoles to nitroalkene derivatives. The transformation occurs at a low catalyst loading of 5 mol%, allowing for the synthesis of nitroalkanes with good yields and functional group tolerance.

Activation of the Aromatic Core of 3,3'-(Pyridine-2,6-diylbis(1H-1,2,3-triazole-4,1-diyl))bis(propan-1-ol)-Effects on Extraction Performance, Stability Constants, and Basicity.

The "CHON" compatible water-soluble ligand 3,3'-(pyridine-2,6-diylbis(1H-1,2,3-triazole-4,1-diyl))bis(propan-1-ol) (PTD) has shown promise for selectively stripping actinide ions from an organic phase containing both actinide and lanthanide ions, by preferential complexation of the former. Aiming at improving its complexation properties, PTD-OMe was synthesized, bearing a methoxy group on the central pyridine ring, thus increasing its basicity and hence complexation strength. Unfortunately, solvent extraction experiments in the range of 0.1-1 mol/L nitric acid proved PTD-OMe to be less efficient than PTD. This behavior is explained by its greater pKa value (pKa = 2.54) compared to PTD (pKa = 2.1). This counteracts its improved complexation properties for Cm(III) (log ß3(PTD-OMe) = 10.8 ± 0.4 versus log ß3(PTD) = 9.9 ± 0.5).

Redox-Switchable Calix[6]arene-Based Isomeric Rotaxanes.

Operating molecular machines are based on switchable systems whose components can be set in motion in a controllable fashion. The presence of nonsymmetrical elements is a mandatory requirement to obtain and demonstrate the unidirectionality of motion. Calixarene-based macrocycles have proved to be very efficient hosts in the design of oriented rotaxanes and of pseudorotaxanes with strict control over the direction of complexation. A series of two-station rotaxanes based on bipyridinium-ammonium axles was synthesized and characterized. A recently reported supramolecularly assisted strategy for the synthesis of different orientational isomers was exploited, and the ammonium unit was identified as a proper secondary station for the calixarene. Displacement of the macrocycle was triggered by electrochemical reduction of the bipyridinium primary station, and it was shown that the shuttling is influenced both by the length of the chain of the axle component and by the position of the secondary station with respect to the calixarene rims.

Electrochemically Triggered Co-Conformational Switching in a [2]catenane Comprising a Non-Symmetric Calix[6]arene Wheel and a Two-Station Oriented Macrocycle.

Catenanes with desymmetrized ring components can undergo co-conformational rearrangements upon external stimulation and can form the basis for the development of molecular rotary motors. We describe the design, synthesis and properties of a [2]catenane consisting of a macrocycle-the 'track' ring-endowed with two distinct recognition sites (a bipyridinium and an ammonium) for a calix[6]arene-the 'shuttle' ring. By exploiting the ability of the calixarene to thread appropriate non-symmetric axles with directional selectivity, we assembled an oriented pseudorotaxane and converted it into the corresponding oriented catenane by intramolecular ring closing metathesis. Cyclic voltammetric experiments indicate that the calixarene wheel initially surrounds the bipyridinium site, moves away from it when it is reduced, and returns in the original position upon reoxidation. A comparison with appropriate model compounds shows that the presence of the ammonium station is necessary for the calixarene to leave the reduced bipyridinium site.

Time-Resolved Laser Fluorescence Spectroscopy Study of the Coordination Chemistry of a Hydrophilic CHON [1,2,3-Triazol-4-yl]pyridine Ligand with Cm(III) and Eu(III).

The complexation of Cm(III) and Eu(III) with the novel i-SANEX complexing agent 2,6-bis[1-(propan-1-ol)-1,2,3-triazol-4-yl]pyridine (PTD) was studied by time-resolved laser fluorescence spectroscopy (TRLFS). The formation of 1:3, 1:2, and 1:1 metal/ligand complexes was identified upon increasing PTD concentration in 10-3 mol/L HClO4 and in 0.44 mol/L HNO3 solutions. For all these complexes, stability constants were determined at different acid concentrations. Though under the extraction conditions proposed for an An/Ln separation process, that is, for 0.08 mol/L PTD in 0.44 mol/L HNO3, 1:3 complexes represent the major species, a significant fraction of 1:2 complexes was found. This is caused by ligand protonation, and results in lower Eu(III)/Am(III) separation factors compared to SO3-Ph-BTP, until now considered the i-SANEX reference ligand. Focused extraction studies performed at lower proton concentration, where the 1:3 complex is formed exclusively, confirm this assumption.

Efficient active-template synthesis of calix[6]arene-based oriented pseudorotaxanes and rotaxanes.

A substrate can modify its chemical features, including a change of its reactivity, as a consequence of non-covalent interactions upon inclusion within a molecular host. Since the rise of supramolecular chemistry, this phenomenon has stimulated the ingenuity of scientists to emulate the function of enzymes by designing supramolecular systems in which the energetics and selectivity of reactions can be manipulated through programmed host-guest interactions and/or steric confinement. In this paper we investigate how the engulfment of a positively charged pyridinium-based guest inside the π-rich cavity of a tris-(N-phenylureido)calix[6]arene host affects its reactivity towards a SN2 reaction. We found that the alkylation of complexed substrates leads to the formation of pseudorotaxanes and rotaxanes with faster kinetics and higher yields with respect to the standard procedures exploited so far. More importantly, the strategy described here expands the range of efficient synthetic routes for the formation of mechanically interlocked species with a strict control of the mutual orientation of their non-symmetric molecular components.

Hydrophilic Clicked 2,6-Bis-triazolyl-pyridines Endowed with High Actinide Selectivity and Radiochemical Stability: Toward a Closed Nuclear Fuel Cycle.

There is still an evident need for selective and stable ligands able to separate actinide(III) from lanthanide(III) metal ions in view of the treatment of the accumulated radioactive waste and of the recycling of minor actinides. We have herein demonstrated that hydrophilic 2,6-bis-triazolyl-pyridines are able to strip all actinides in all the different oxidation states from a diglycolamide-containing kerosene solution into an acidic aqueous phase. The ascertained high actinide selectivity, efficiency, extraction kinetics, and chemical/radiolytic stability spotlight this hydrophilic class of ligands as exceptional candidates for advanced separation processes fundamental for closing the nuclear fuel cycle and solving the environmental issues related to the management of existing nuclear waste.

Calix[4]arene-Functionalised Silver Nanoparticles as Hosts for Pyridinium-Loaded Gold Nanoparticles as Guests.

A series of lipophilic gold nanoparticles (AuNPs) circa 5 nm in diameter and having a mixed organic layer consisting of 1-dodecanethiol and 1-(11-mercaptoundecyl) pyridinium bromide was synthesised by reacting tetraoctylammonium bromide stabilised AuNPs in toluene with different mixtures of the two thiolate ligands. A bidentate ω-alkylthiolate calix[4]arene derivative was instead used as a functional protecting layer on AgNPs of approximately 3 nm. The functionalised nanoparticles were characterised by transmission electron microscopy (TEM), and by UV/Vis and X-ray photoelectron spectroscopy (XPS). Recognition of the pyridinium moieties loaded on the AuNPs by the calix[4]arene units immobilised on the AgNPs was demonstrated in solution of weakly polar solvents by UV/Vis titrations and DLS measurements. The extent of Au-AgNPs aggregation, shown through the low-energy shift of their surface plasmon bands (SPB), was strongly dependent on the loading of the pyridinium moieties present in the organic layer of the AuNPs. Extensive aggregation between dodecanethiol-capped AuNPs and the Ag calix[4]arene-functionalised NPs was also promoted by the action of a simple N-octyl pyridinium difunctional supramolecular linker. This linker can interdigitate through its long fatty tail in the organic layer of the dodecanethiol-capped AuNPs, and simultaneously interact through its pyridinium moiety with the calix[4]arene units at the surface of the modified AgNPs.

Toward directionally controlled molecular motions and kinetic intra- and intermolecular self-sorting: threading processes of nonsymmetric wheel and axle components.

We have investigated the self-assembly of pseudorotaxanes composed of viologen-type axle and calix[6]arene wheel components. The distinctive feature of this system is that both components are structurally nonsymmetric; hence, their self-assembly can follow four distinct pathways and eventually give rise to two different orientational pseudorotaxane isomers. We found that the alkyl side chains of the viologen recognition site on the molecular axle act as strict kinetic control elements in the self-assembly, thereby dictating which side of the axle pierces the calixarene cavity. Specifically, nonsymmetric axles with alkyl side chains of different length thread the wheel with the shorter chain. Such a selectivity, in combination with the face-selective threading of viologen-type axles afforded by tris(N-phenylureido)calix[6]arenes, enables a strict directional control of the self-assembly process for both the face of the wheel and the side of the axle. This kinetic selectivity allows both intramolecular self-sorting between two different side chains in a nonsymmetric axle and intermolecolar self-sorting among symmetric axles with alkyl substituents of different length.

Assembly of gold nanoparticles on functionalized Si(100) surfaces through pseudorotaxane formation.

The assembly of gold nanoparticles (AuNPs) on a hydrogenated Si(100) surface, mediated by a series of hierarchical and reversible complexation processes, is reported. The proposed multi-step sequence involves a redox-active ditopic guest and suitable calix[n]arene-based hosts, used as functional organic monolayers of the two inorganic components. Surface reactions and controlled release of AuNPs have been monitored by application of XPS, atomic force microscopy (AFM), field-emission scanning electron microscopy (FESEM) and electrochemistry.

Hierarchical self-assembly of amphiphilic calix[6]arene wheels and viologen axles in water.

We have designed and synthesized two amphiphilic calix[6]arene derivatives, CA8 and CA18, that combine the potential to act as wheel components for pseudorotaxane structures with the self-assembly features typical of surfactant molecules in aqueous solution. Their endo-cavity recognition and selfaggregation properties were compared with those of a non-amphiphilic analogue, C8. TEM, DLS, and fluorescence experiments show that in water the amphiphilic calixarenes form vesicle- and micelle-like aggregates. The size, nature and properties of such aggregates depend on the length of the alkyl chain anchored at the lower rim of the calix[6]arene skeleton, as well as on the inclusion of a molecular guest into the wheel. Specifically, the release of a fluorescent guest entrapped inside the CA8 vesicles is accelerated in the presence of dioctylviologen axles that can pierce the calixarene cavity.

Solvent- and light-controlled unidirectional transit of a nonsymmetric molecular axle through a nonsymmetric molecular wheel.

The development of a pseudorotaxane motif capable of performing unidirectional threading and dethreading processes under control of external stimuli is particularly important for the construction of processive linear motors based on rotaxanes and, at least in principle, it discloses the possibility to access to rotary motors based on catenanes. Here, we report a strategy to obtain the solvent-controlled unidirectional transit of a molecular axle through a molecular wheel. It is based on the use of appropriately designed molecular components, the essential feature of which is their non-symmetric structure. Specifically they are an axle containing a central electron-acceptor 4,4'-bipyridinium core functionalized with a hexanol chain at one side, and a stilbene unit connected through a C6 chain at the other side, and a heteroditopic tris(phenylureido)-calix[6]arene wheel. In apolar solvents the axle threads into the wheel from its upper rim and with the end carrying the OH group, giving an oriented pseudorotaxane structure. After a stoppering reaction, which replaces the small hydroxy group with a bulky diphenylacetyl moiety, and replacement of the apolar solvent with a polar one, dethreading occurs through the slippage of the stilbene unit from the lower rim of the wheel, that is, in the same direction of the threading process. The essential role played by the stilbene unit to achieve the unidirectional transit of the axle through the wheel, and to tune the dethreading rate by light is also demonstrated.