Structures, vibrational frequencies, and stabilities of halogen cluster anions and cations, X(n)(+/-), n = 3, 4, and 5.

The structures, vibrational frequencies, and thermodynamic stabilities of the homonuclear polyhalogen ions, X3(+), X3(-), X4(+), X4(-), X5(+), and X5(-) (X = Cl, Br, I), have been calculated at the CCSD(T) level. The energetics were calculated using the Feller-Peterson-Dixon approach for the prediction of reliable enthalpies of formation. The calculations allow the following predictions where stabilities are defined in terms of thermodynamic quantities.

Supramolecular guests in solvent driven block copolymer assembly: From internally structured nanoparticles to micelles.

Supramolecular interactions between different hydrogen-bonding guests and poly(2-vinyl pyridine)--poly (styrene) can be exploited to prepare remarkably diverse self-assembled nanostructures in dispersion from a single block copolymer (BCP). The characteristics of the BCP can be efficiently controlled by tailoring the properties of a guest which preferentially binds to the P2VP block. For example, the incorporation of a hydrophobic guest creates a hydrophobic BCP complex that forms phase separated nanoparticles upon self-assembly.

Linear versus dendritic molecular binders for hydrogel network formation with clay nanosheets: studies with ABA triblock copolyethers carrying guanidinium ion pendants.

ABA-triblock copolyethers 1a-1c as linear polymeric binders, in combination with clay nanosheets (CNSs), afford high-water-content moldable supramolecular hydrogels with excellent mechanical properties by constructing a well-developed crosslinked network in water. The linear binders carry in their terminal A blocks guanidinium ion (Gu(+)) pendants for adhesion to the CNS surface, while their central B block comprises poly(ethylene oxide) (PEO) that serves as a flexible linker for adhered CNSs. Although previously reported dendritic binder 2 requires multistep synthesis and purification, the linear binders can be obtained in sizable quantities from readily available starting materials by controlled polymerization.

Mesostructured Block Copolymer Nanoparticles: Versatile Templates for Hybrid Inorganic/Organic Nanostructures.

We present a versatile strategy to prepare a range of nanostructured poly(styrene)-block-poly(2-vinyl pyridine) copolymer particles with tunable interior morphology and controlled size by a simple solvent exchange procedure. A key feature of this strategy is the use of functional block copolymers incorporating reactive pyridyl moieties which allow the absorption of metal salts and other inorganic precursors to be directed. Upon reduction of the metal salts, well-defined hybrid metal nanoparticle arrays could be prepared, while the use of oxide precursors followed by calcination permits the synthesis of silica and titania particles.

Improved performance of protected catecholic polysiloxanes for bioinspired wet adhesion to surface oxides.

A facile synthetic strategy for introducing catecholic moieties into polymeric materials based on a readily available precursor (eugenol) and efficient chemistries [tris(pentafluorophenyl)borane-catalyzed silation and thiol-ene coupling] is reported. Silyl protection is shown to be critical for the oxidative stability of catecholic moieties during synthesis and processing, which allows functionalized polysiloxane derivatives to be fabricated into 3D microstructures as well as 2D patterned surfaces. Deprotection gives stable catechol surfaces whose adhesion to a variety of oxide surfaces can be precisely tuned by the level of catechol incorporation.

High hopes: can molecular electronics realise its potential?

Manipulating and controlling the self-organisation of small collections of molecules, as an alternative to investigating individual molecules, has motivated researchers bent on processing and storing information in molecular electronic devices (MEDs). Although numerous ingenious examples of single-molecule devices have provided fundamental insights into their molecular electronic properties, MEDs incorporating hundreds to thousands of molecules trapped between wires in two-dimensional arrays within crossbar architectures offer a glimmer of hope for molecular memory applications. In this critical review, we focus attention on the collective behaviour of switchable mechanically interlocked molecules (MIMs)--specifically, bistable rotaxanes and catenanes--which exhibit reset lifetimes between their ON and OFF states ranging from seconds in solution to hours in crossbar devices.

Donor-acceptor ring-in-ring complexes.

The self-assembly of three donor-acceptor ring-in-ring complexes, prepared from the π-electron-deficient tetracationic cyclophane, cyclobis(paraquat-4,4'-biphenylene), and three large π-electron-rich crown ethers (each 50-membered rings) containing dioxynaphthalene (DNP) and tetrathiafulvalene (TTF) units in pairs (DNP/DNP, DNP/TTF and TTF/TTF), is reported. (1)H NMR spectroscopic analyses are indicative of the formation of 1:1 complexes in CD(3)CN, whilst the charge-transfer interactions between the DNP and TTF units of the crown ethers and the tetracationic cyclophane have permitted the measurement of binding constants of up to 4×10(3) M(-1) in CH(3)CN to be made using UV/Vis spectroscopy. Ring-in-ring complexes are proposed as intermediates in the stepwise synthesis of molecular Borromean rings (BRs) comprised of three different rings.

Reactive, multifunctional polymer films through thermal cross-linking of orthogonal click groups.

The ability to produce robust and functional cross-linked materials from soluble and processable organic polymers is dependent upon facile chemistries for both reinforcing the structure through cross-linking and for subsequent decoration with active functional groups. Generally, covalent cross-linking of polymeric assemblies is brought about by the application of heat or light to generate highly reactive groups from stable precursors placed along the chains that undergo coupling or grafting reactions. Typically, these strategies suffer from a general lack of control of the cross-linking chemistry as well as the fleeting nature of the reactive species that precludes secondary chemistry.

Monofunctionalized pillar[5]arene as a host for alkanediamines.

Alkanediamines serve as neutral guests for the recently discovered host pillar[5]arene. The proposed [2]pseudorotaxane nature of the superstructure of the 1:1 host-guest complexes is supported by the template-directed synthesis of a related [2]rotaxane. A synthetic route to monofunctional pillar[5]arenes has also been developed, allowing for the creation of a fluorescent sensor for alkylamine binding.

Mechanically stabilized tetrathiafulvalene radical dimers.

Two donor-acceptor [3]catenanes-composed of a tetracationic molecular square, cyclobis(paraquat-4,4'-biphenylene), as the π-electron deficient ring and either two tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) containing macrocycles or two TTF-butadiyne-containing macrocycles as the π-electron rich components-have been investigated in order to study their ability to form TTF radical dimers. It has been proven that the mechanically interlocked nature of the [3]catenanes facilitates the formation of the TTF radical dimers under redox control, allowing an investigation to be performed on these intermolecular interactions in a so-called "molecular flask" under ambient conditions in considerable detail. In addition, it has also been shown that the stability of the TTF radical-cation dimers can be tuned by varying the secondary binding motifs in the [3]catenanes.

Highly stable tetrathiafulvalene radical dimers in [3]catenanes.

Two [3]catenane 'molecular flasks' have been designed to create stabilized, redox-controlled tetrathiafulvalene (TTF) dimers, enabling their spectrophotometric and structural properties to be probed in detail. The mechanically interlocked framework of the [3]catenanes creates the ideal arrangement and ultrahigh local concentration for the encircled TTF units to form stable dimers associated with their discrete oxidation states. These dimerization events represent an affinity umpolung, wherein the inversion in electronic affinity replaces the traditional TTF-bipyridinium interaction, which is over-ridden by stabilizing mixed-valence (TTF)2•+ and radical-cation (TTF•+)2 states inside the 'molecular flasks.

A push-button molecular switch.

The preparation, characterization, and switching mechanism of a unique single-station mechanically switchable hetero[2]catenane are reported. The facile synthesis utilizing a "threading-followed-by-clipping" protocol features Cu(2+)-catalyzed Eglinton coupling as a mild and efficient route to the tetrathiafulvalene-based catenane in high yield. The resulting mechanically interlocked molecule operates as a perfect molecular switch, most readily described as a "push-button" switch, whereby two discrete and fully occupied translational states are toggled electrochemically at incredibly high rates.

Acid-base actuation of [c2]daisy chains.

A versatile synthetic strategy, which was conceived and employed to prepare doubly threaded, bistable [c2]daisy chain compounds, is described. Propargyl and 1-pentenyl groups have been grafted onto the stoppers of [c2]daisy chain molecules obtained using a template-directed synthetic protocol. Such [c2]daisy chain molecules undergo reversible extension and contraction upon treatment with acid and base, respectively.

Heterogeneous catalysis of a copper-coated atomic force microscopy tip for direct-write click chemistry.

We report a constructive scanning probe lithography method that uses heterogeneous copper-coated atomic force microscopy tips to catalyze azide-alkyne cycloadditions (CuAAC) between solvated terminal alkyne molecules and azide-terminated self-assembled monolayers on silicon surfaces. Spatially controlled surface functionalization was carried out successfully with 50 mM ethanolic solutions of small molecules bearing terminal alkyne groups--propargylamine, 4-pentynoic acid, and an alkynyl-oligoethyleneoxide. We observed that reaction occurs only where the copper tip is in contact with an azide-terminated surface resulting in features with linewidths on the order of 50 nm.

Complexation between methyl viologen (paraquat) bis(hexafluorophosphate) and dibenzo[24]crown-8 revisited.

Paraquat bis(hexafluorophosphate) undergoes stepwise dissociation in acetone. All three species-the neutral molecule, and the mono- and dications-are represented significantly under the experimental conditions typically used in host-guest binding studies. Paraquat forms at least four host-guest complexes with dibenzo[24]crown-8.

Kinetic and thermodynamic approaches for the efficient formation of mechanical bonds.

Among the growing collection of molecular systems under consideration for nanoscale device applications, mechanically interlocked compounds derived from electrochemically switchable bistable [2]rotaxanes and [2]catenanes show great promise. These systems demonstrate dynamic, relative movements between their components, such as shuttling and circumrotation, enabling them to serve as stimuli-responsive switches operated via reversible, electrochemical oxidation-reduction rather than through the addition of chemical reagents. Investigations into these systems have been intense for a number of years, yet limitations associated with their synthesis have hindered incorporation of their mechanical bonds into more complex architectures and functional materials.

A one-pot synthesis of constitutionally unsymmetrical rotaxanes using sequential Cu(I)-catalyzed azide-alkyne cycloadditions.

A one-pot sequential Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) strategy is presented for the synthesis of constitutionally unsymmetrical cyclobis(paraquat-p-phenylene)-based rotaxanes in good yields from simple starting materials. The methodology consists of performing multiple CuAAC reactions to stopper a pseudorotaxane in a stepwise manner, the order of which is controlled through silyl-protection and Ag(I)-catalyzed deprotection of a terminal alkyne. The methodology is highlighted by the synthesis of an amphiphilic branched [4]rotaxane.

Synthesis of, and structural assignments to the stereoisomers of bis (2,2')- and tris (2,2',2")-tetrahydrofurans: conformational features and ionic binding capacities of these gateway polycyclic networks.

Construction of the polytetrahydrofuranyl building blocks 6-10 from the common bissiloxyacetone precursor 11 is detailed. The approach is concise and, for the bis-(THF) pair, capitalizes on the full retention of configuration observed during the rhodium-promoted decarbonylation of aldehydes 18 and 19. The capability of the title compounds to associate with alkali metal ions in solution and the gas phase has demonstrated a preference for Li+ over Na+ and K+ in all cases, with 6 and 7 exhibiting somewhat higher binding selectivities than 8-10.

Modular synthesis and dynamics of a variety of donor-acceptor interlocked compounds prepared by click chemistry.

A series of donor-acceptor [2]-, [3]-, and [4]rotaxanes and self-complexes ([1]rotaxanes) have been synthesized by a threading-followed-by-stoppering approach, in which the precursor pseudorotaxanes are fixed by using Cu(I)-catalyzed Huisgen 1,3-dipolar cycloaddition to attach the required stoppers. This alternative approach to forming rotaxanes of the donor-acceptor type, in which the donor is a 1,5-dioxynaphthalene unit and the acceptor is the tetracationic cyclophane cyclobis(paraquat-p-phenylene), proceeds with enhanced yields relative to the tried and tested synthetic strategies, which involve the clipping of the cyclophane around a preformed dumbbell containing pi-electron-donating recognition sites. The new synthetic approach is amenable to application to highly convergent sequences.

Efficient templated synthesis of donor-acceptor rotaxanes using click chemistry.

The mild reaction conditions, remarkable functional group compatibility, and complete regioselectivity of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition ("click chemistry") between organic azides and terminal alkynes have led to a threading-followed-by-stoppering approach to the synthesis of donor-acceptor rotaxanes incorporating cyclobis(paraquat-p-phenylene) (CBPQT4+) as the pi-accepting ring component. Rotaxane formation is initiated by reacting azide-functionalized pseudorotaxanes containing pi-donating 1,5-dioxynaphthalene (DNP) recognition units with appropriate alkyne-functionalized stoppers. The high yields obtained in this efficient, kinetically controlled post-assembly covalent modification, as well as the excellent convergence of the synthetic protocol, are demonstrated by the preparation of [2]-, [3]-, and [4]rotaxanes containing multiple DNP/CBPQT4+ donor-acceptor recognition motifs.