Monica Semeraro

Probing Donor−Acceptor Interactions and Co-Conformational Changes in Redox Active Desymmetrized [2]Catenanes

We describe the synthesis and characterization of a series of desymmetrized donor-acceptor [2]catenanes where different donor and acceptor units are assembled within a confined catenated geometry. Remarkable translational selectivity is maintained in all cases, including two fully desymmetrized [2]catenanes where both donors and acceptors are different, as revealed by X-ray crystallography in the solid state, and by (1)H NMR spectroscopy and electrochemistry in solution. In all desymmetrized [2]catenanes the co-conformation is dominated by the strongest donor and acceptor pairs, whose charge-transfer interactions also determine the visible absorption properties. Voltammetric and spectroelectrochemical experiments show that the catenanes can be reversibly switched among as many as seven states, characterized by distinct electronic and optical properties, by electrochemical stimulation in a relatively narrow and easily accessible potential window. Moreover in some of these compounds the oxidation of the electron donor units or the reduction of the electron acceptor ones causes the circumrotation of one molecular ring with respect to the other. These features make these compounds appealing for the development of molecular electronic devices and mechanical machines.

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.

A comparison of shuttling mechanisms in two constitutionally isomeric bistable rotaxane-based sunlight-powered nanomotors

To find out how best to optimize shuttling of the macrocycle in a particular class of photochemically driven molecular abacus, which has the molecular structure of BR-I6+ in its Mark I prototype (Ashton et al., Chem. Eur. J. 2000, 6, 3558), we have synthesized and characterized a Mark II version of this kind of two-station rotaxane comprised of six molecular modules, namely (a) a bisparaphenylene[34]crown-10 electron donor macrocycle M and its dumbbell-shaped component which contains (b) a Ru(ii)-polypyridine photoactive unit P2+ as one of its stoppers, (c) a p-terphenyl-type ring system as a rigid spacer S, (d) 4,4′-bipyridinium (A12+) and (e) 3,3′-dimethyl-4,4′-bipyridinium (A22+) electron acceptor units that can play the role of stations for the macrocycle M, and (f) a tetraarylmethane group T as the second stopper. This Mark II version is identical with BR-I6+ in the Mark I series that works as a sunlight-powered nanomotor (Balzani et al., Proc. Natl. Acad. Sci. USA 2006, 103, 1178), except for the swapping of the two stations A12+ and A22+ along the dumbbell-shaped component, i.e. the Mark I and II bistable rotaxanes are constitutionally isomeric. We have found the closer the juxtaposition of the electron transfer photosensitizer P2+ to the better (A12+) of the two electron acceptors, namely the situation in BR-II6+ compared with that in BR-I6+ results in an increase in the rate — and hence the efficiency — of the photoinduced electron-transfer step. The rate of the back electron transfer, however, also increases. As a consequence, BR-II6+ performs better than BR-I6+ in the fuel-assisted system, but much worse when it is powered by visible light (e.g. sunlight) alone. By contrast, when shuttling is electrochemically driven, the only difference between the two bistable rotaxanes in the Mark I and Mark II series is that the macrocycle M moves in opposite directions.

Self-Assembly of Calix[6]arene-Diazapyrenium Pseudorotaxanes: Interplay of Molecular Recognition and Ion-Pairing Effects

The calix[6]arene wheel CX forms pseudorotaxane species with the diazapyrenium-based axle 1.2PF(6) in CH(2)Cl(2) solution. The macrocyclic component is a heteroditopic receptor, which can complex the electron-acceptor moiety of the axle inside its cavity and the counterions with the ureidic groups on the upper rim. The self-assembled supramolecular species is a complex structure, which involves three components--the wheel, the axle and its counterions--that can mutually interact and affect. The stoichiometry of the resulting supramolecular complex depends on the nature and concentration of the counterions. Namely, it is observed that in dilute solution and with low-coordinating anions the axle takes two wheels, whereas with highly coordinating anions or in concentrated solutions the complex has a 1:1 stoichiometry.

Light Control of Stoichiometry and Motion in Pseudorotaxanes Comprising a Cucurbit[7]uril Wheel and an Azobenzene-Bipyridinium Axle

Pseudorotaxanes are the simplest prototypes for the construction of molecular machines based on threaded species. Investigation on molecular motions in these model systems is a necessary action for an efficient design of working molecular machines and motors. Herein we report on photoactive pseudorotaxanes based on the interaction between bipyridinium and cucurbit[7]uril (CB7). The molecular axle is composed of a central bipyridinium unit and two azobenzene moieties at the extremities. CB7 can form two different complexes with this molecule: a [2]pseudorotaxane, in which the macrocycle shuttles fast along the length of the axle, and a [3]pseudorotaxane, in which two CB7 s are confined at the extremities of the axle. Upon trans to cis isomerization of the azobenzene moieties, the [3]pseudorotaxane is destabilized, and only one CB7 resides on the axle, surrounding the bipyridinium unit. The system was successfully inserted into the core of liposomes, and preliminary investigations confirmed that it maintains its switching ability.

Electrochemically Controlled Formation/Dissociation of Phosphonate‐Cavitand/Methylpyridinium Complexes

The phosphorus-bridged cavitand 1 self-assembles very efficiently in CH2Cl2 with either the monopyridinium guest 2+ or the bispyridinium guest 3(2+). In the first case a 1:1 complex is obtained, whereas in the second case both 1:1 and 2:1 host-guest complexes are observed. The association between 1 and either one of the guests causes the quenching of the cavitand fluorescence; in the case of the adduct between 1 and 3(2+), the fluorescence of the latter is also quenched. Cavitand complexation is found to affect the reduction potential values of the electroactive guests. Voltammetric and spectroelectrochemical measurements show that upon one-electron reduction both guests are released from the cavity of 1. Owing to the chemical reversibility of such redox processes, the supramolecular complexes can be re-assembled upon removal of the extra electron from the guest. Systems of this kind are promising for the construction of switchable nanoscale devices and self-assembling supramolecular materials, the structure and properties of which can be reversibly controlled by electrochemical stimuli.

Redox control of molecular motion in switchable artificial nanoscale devices.

The design, synthesis, and operation of molecular-scale systems that exhibit controllable motions of their component parts is a topic of great interest in nanoscience and a fascinating challenge of nanotechnology. The development of this kind of species constitutes the premise to the construction of molecular machines and motors, which in a not-too-distant future could find applications in fields such as materials science, information technology, energy conversion, diagnostics, and medicine. In the past 25 years the development of supramolecular chemistry has enabled the construction of an interesting variety of artificial molecular machines. These devices operate via electronic and molecular rearrangements and, like the macroscopic counterparts, they need energy to work as well as signals to communicate with the operator. Here we outline the design principles at the basis of redox switching of molecular motion in artificial nanodevices. Redox processes, chemically, electrically, or photochemically induced, can indeed supply the energy to bring about molecular motions. Moreover, in the case of electrically and photochemically induced processes, electrochemical and photochemical techniques can be used to read the state of the system, and thus to control and monitor the operation of the device. Some selected examples are also reported to describe the most representative achievements in this research area.

Tuning Fluorescence Lifetimes through Changes in Herzberg−Teller Activities: The Case of Triphenylene and Its Hexamethoxy-Substituted Derivative

The fluorescence spectra of triphenylene (TP) and 2,3,6,7,10,11-hexamethoxy-triphenylene (HMTP) are measured in glass matrices, and the vibronic structure associated with the electronic spectra is simulated with the help of quantum chemically computed molecular parameters. Franck-Condon (FC) and Herzberg-Teller (HT) mechanisms are included. For excited-state calculations, both configuration interaction with single excitations (CIS) and time-dependent density functional theory (TDDFT) are employed. It is shown that the FC activity is associated with modes of similar shape and frequency in both molecules, while the HT-induced false origins with the largest activity are associated with rather different frequencies and normal coordinates as a result of the mixing and energy lowering of the low-lying allowed excited states in HMTP. The increased HT activity explains the reduced S(1) state lifetime in the substituted TP, in turn driven by the excited-state rearrangement occurring upon substitution of the TP core.

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.

Artificial molecular machines driven by light.

The bottom-up construction and operation of machines and motors of molecular size is a topic of great interest in nanoscience, and a fascinating challenge of nanotechnology. The problem of the energy supply to make molecular machines work is of the greatest importance. Research in the last ten years has demonstrated that light energy can be used to power artificial nanomachines by exploiting photochemical processes in appropriately designed systems. More recently, it has become clear that under many aspects light is the best choice to power molecular machines; for example, systems that show autonomous operation and do not generate waste products can be obtained. This review is intended to discuss the design principles at the basis of light-driven artificial nanomachines, and provide an up-to-date overview on the prototype systems that have been developed.