Rupturing aromaticity by periphery overcrowding.

The balance between strain relief and aromatic stabilization dictates the form and function of non-planar π-aromatics. Overcrowded systems are known to undergo geometric deformations, but the energetically favourable π-electron delocalization of their aromatic ring(s) is typically preserved. In this study we incremented the strain energy of an aromatic system beyond its aromatic stabilization energy, causing it to rearrange and its aromaticity to be ruptured. We noted that increasing the steric bulk around the periphery of π-extended tropylium rings leads them to deviate from planarity to form contorted conformations in which aromatic stabilization and strain are close in energy. Under increasing strain, the aromatic π-electron delocalization of the system is broken, leading to the formation of a non-aromatic, bicyclic analogue referred to as 'Dewar tropylium'. The aromatic and non-aromatic isomers have been found to exist in rapid equilibrium with one another. This investigation demarcates the extent of steric deformation tolerated by an aromatic carbocycle and thus provides direct experimental insights into the fundamental nature of aromaticity.

Enhancing the Efficiency of a Dye-Sensitized Solar Cell Based on a Metal Oxide Nanocomposite Gel Polymer Electrolyte.

To overcome the critical limitations of liquid-electrolyte-based dye-sensitized solar cells, quasi-solid-state electrolytes have been explored as a means of addressing long-term device stability, albeit with comparatively low ionic conductivities and device performances. Although metal oxide additives have been shown to augment ionic conductivity, their propensity to aggregate into large crystalline particles upon high-heat annealing hinders their full potential in quasi-solid-state electrolytes. In this work, sonochemical processing has been successfully applied to generate fine Co3O4 nanoparticles that are highly dispersible in a PAN:P(VP-co-VAc) polymer-blended gel electrolyte, even after calcination. An optimized nanocomposite gel polymer electrolyte containing 3 wt % sonicated Co3O4 nanoparticles (PVVA-3) delivers the highest ionic conductivity (4.62 × 10-3 S cm-1) of the series. This property is accompanied by a 51% enhancement in the apparent diffusion coefficient of triiodide versus both unmodified and unsonicated electrolyte samples. The dye-sensitized solar cell based on PVVA-3 displays a power conversion efficiency of 6.46% under AM1.5 G, 100 mW cm-2. By identifying the optimal loading of sonochemically processed nanoparticles, we are able to generate a homogenous extended particle network that effectively mobilizes redox-active species through a highly amorphous host matrix. This effect is manifested in a selective 51% enhancement in photocurrent density (JSC = 16.2 mA cm-2) and a lowered barrier to N719 dye regeneration (RCT = 193 Ω) versus an unmodified solar cell. To the best of our knowledge, this work represents the highest known efficiency to date for dye-sensitized solar cells based on a sonicated Co3O4-modified gel polymer electrolyte. Sonochemical processing, when applied in this manner, has the potential to make meaningful contributions toward the ongoing mission to achieve the widespread exploitation of stable and low-cost dye-sensitized solar cells.

Excited-State Aromatic Interactions in the Aggregation-Induced Emission of Molecular Rotors.

Small, apolar aromatic groups, such as phenyl rings, are commonly included in the structures of fluorophores to impart hindered intramolecular rotations, leading to desirable solid-state luminescence properties. However, they are not normally considered to take part in through-space interactions that influence the fluorescent output. Here, we report on the photoluminescence properties of a series of phenyl-ring molecular rotors bearing three, five, six, and seven phenyl groups. The fluorescent emissions from two of the rotors are found to originate, not from the localized excited state as one might expect, but from unanticipated through-space aromatic-dimer states. We demonstrate that these relaxed dimer states can form as a result of intra- or intermolecular interactions across a range of environments in solution and solid samples, including conditions that promote aggregation-induced emission. Computational modeling also suggests that the formation of aromatic-dimer excited states may account for the photophysical properties of a previously reported luminogen. These results imply, therefore, that this is a general phenomenon that should be taken into account when designing and interpreting the fluorescent outputs of luminescent probes and optoelectronic devices based on fluorescent molecular rotors.

Asymmetric Anion-π Catalysis of Iminium/Nitroaldol Cascades To Form Cyclohexane Rings with Five Stereogenic Centers Directly on π-Acidic Surfaces.

Anion-π interactions have been introduced to catalysis only recently, and evidence for their significance is so far limited to one classical model reaction in enolate and enamine chemistry. In this report, asymmetric anion-π catalysis is achieved for the first time for a more demanding cascade process. The selected example affords six-membered carbocycles with five stereogenic centers in a single step from achiral and acyclic substrates. Rates, yields, turnover, diastereo- and enantioselectivity are comparable with conventional catalysts. Rates and stereoselectivity increase with the π-acidity of the new anion-π catalysts. Further support for operational anion-π interactions in catalysis is obtained from inhibition with nitrate. As part of the stereogenic cascade reaction, iminium chemistry and conjugate additions are added to the emerging repertoire of asymmetric anion-π catalysis.

Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces.

To integrate anion-π, cation-π, and ion pair-π interactions in catalysis, the fundamental challenge is to run reactions reliably on aromatic surfaces. Addressing a specific question concerning enolate addition to nitroolefins, this study elaborates on Leonard turns to tackle this problem in a general manner. Increasingly refined turns are constructed to position malonate half thioesters as close as possible on π-acidic surfaces. The resulting preorganization of reactive intermediates is shown to support the disfavored addition to enolate acceptors to an absolutely unexpected extent. This decisive impact on anion-π catalysis increases with the rigidity of the turns. The new, rigidified Leonard turns are most effective with weak anion-π interactions, whereas stronger interactions do not require such ideal substrate positioning to operate well. The stunning simplicity of the motif and its surprisingly strong relevance for function should render the introduced approach generally useful.

Asymmetric Anion-π Catalysis: Enamine Addition to Nitroolefins on π-Acidic Surfaces.

Here we provide experimental evidence for anion-π catalysis of enamine chemistry and for asymmetric anion-π catalysis. A proline for enamine formation on one side and a glutamic acid for nitronate protonation on the other side are placed to make the enamine addition to nitroolefins occur on the aromatic surface of π-acidic naphthalenediimides. With increasing π acidity of the formally trifunctional catalysts, rate and enantioselectivity of the reaction increase. Mismatched and more flexible controls reveal that the importance of rigidified, precisely sculpted architectures increases with increasing π acidity as well. The absolute configuration of stereogenic sulfoxide acceptors at the edge of the π-acidic surface has a profound influence on asymmetric anion-π catalysis and, if perfectly matched, affords the highest enantio- and diastereoselectivity.

Electrochemically addressable trisradical rotaxanes organized within a metal-organic framework.

The organization of trisradical rotaxanes within the channels of a Zr6-based metal-organic framework (NU-1000) has been achieved postsynthetically by solvent-assisted ligand incorporation. Robust Zr(IV)-carboxylate bonds are forged between the Zr clusters of NU-1000 and carboxylic acid groups of rotaxane precursors (semirotaxanes) as part of this building block replacement strategy. Ultraviolet-visible-near-infrared (UV-Vis-NIR), electron paramagnetic resonance (EPR), and 1H nuclear magnetic resonance (NMR) spectroscopies all confirm the capture of redox-active rotaxanes within the mesoscale hexagonal channels of NU-1000. Cyclic voltammetry measurements performed on electroactive thin films of the resulting material indicate that redox-active viologen subunits located on the rotaxane components can be accessed electrochemically in the solid state. In contradistinction to previous methods, this strategy for the incorporation of mechanically interlocked molecules within porous materials circumvents the need for de novo synthesis of a metal-organic framework, making it a particularly convenient approach for the design and creation of solid-state molecular switches and machines. The results presented here provide proof-of-concept for the application of postsynthetic transformations in the integration of dynamic molecular machines with robust porous frameworks.

Formation of a hetero[3]rotaxane by a dynamic component-swapping strategy.

Acid-catalysed scrambling of the mechanically interlocked components between two different homo[3]rotaxanes, constituted of dumbbells containing two secondary dialkylammonium ion recognition sites encircled by two [24]crown-8 rings, each containing a couple of imine bonds, affords a statistical mixture of a hetero[3]rotaxane along with the two homo[3]rotaxanes, indicating that neither selectivity nor cooperativity is operating during the assembly process.

Gated electron sharing within dynamic naphthalene diimide-based oligorotaxanes.

The controlled self-assembly of well-defined and spatially ordered π-systems has attracted considerable interest because of their potential applications in organic electronics. An important contemporary pursuit relates to the investigation of charge transport across noncovalently coupled components in a stepwise fashion. Dynamic oligorotaxanes, prepared by template-directed methods, provide a scaffold for directing the construction of monodisperse one-dimensional assemblies in which the functional units communicate electronically through-space by way of π-orbital interactions. Reported herein is a series of oligorotaxanes containing one, two, three and four naphthalene diimide (NDI) redox-active units, which have been shown by cyclic voltammetry, and by EPR and ENDOR spectroscopies, to share electrons across the NDI stacks. Thermally driven motions between the neighboring NDI units in the oligorotaxanes influence the passage of electrons through the NDI stacks in a manner reminiscent of the conformationally gated charge transfer observed in DNA.

BODIPY-thiophene copolymers as p-channel semiconductors for organic thin-film transistors.

The synthesis and physicochemical properties of a new class of BODIPY-based donor-acceptor π-conjugated polymers are presented. Solution-processed top-gate/bottom-contact (TG-BC) thin-film transistors on flexible plastic substrates exhibit air-stable p-channel activities with charge carrier mobilities as high as 0.17 cm(2) /V·s and current on/off ratios of 10(5) -10(6) , the highest reported to date for a BODIPY-based semiconductor. The results shown here indicate a significant charge-transport improvement (>10000×) in BODIPY-based polymeric semiconductors, demonstrating its potential in future organic optoelectronic applications.

Organic switches for surfaces and devices.

The pursuit to achieve miniaturization has tantalized researchers across the fields of chemistry, physics, biology, materials science and engineering for over half a century because of its many alluring potential applications. As alternatives to traditional "top-down" manufacturing, "bottom-up" approaches, originating from the (supra)molecular level, have enabled researchers to develop switches which can be manipulated on surfaces at nanoscale dimensions with deft precision using simple external triggers. Once on surfaces, these organic switches have been shown to modulate both the physical and chemical surface properties. In this Progress Report, we shed light on recent advances made in our laboratories towards integrated systems using all-organic switches on a variety of substrates. Design concepts are revealed, as well as the overall impact of all-organic switches on the properties of their substrates, while emphasizing the considerable promise and formidable challenges these advanced composite materials pose when it comes to conferring function on them.

Cooperative self-assembly: producing synthetic polymers with precise and concise primary structures.

The quest to construct mechanically interlocked polymers, which present precise monodisperse primary structures that are produced both consistently and with high efficiencies, has been a daunting goal for synthetic chemists for many years. Our ability to realise this goal has been limited, until recently, by the need to develop synthetic strategies that can direct the formation of the desired covalent bonds in a precise and concise fashion while avoiding the formation of unwanted kinetic by-products. The challenge, however, is a timely and welcome one, as a consequence of, primarily, the potential for mechanically interlocked polymers to act as dynamic (noncovalent) yet robust (covalent) new materials for a wide array of applications. One such strategy which has been employed widely in recent years to address this issue, known as Dynamic Covalent Chemistry (DCC), is a strategy in which reactions operate under equilibrium and so offer elements of "proof-reading" and "error-checking" to the bond forming and breaking processes such that the final product distribution always reflects the thermodynamically most favourable compound. By coupling DCC with template-directed protocols, which utilise multiple weak noncovalent interactions to pre-organise and self-assemble simpler small molecular precursors into their desired geometries prior to covalent bond formation, we are able to produce compounds with highly symmetric, robust and complex topologies that are otherwise simply unobtainable by more traditional methods. Harnessing these strategies in an iterative, step-wise fashion brings us ever so much closer towards perfecting the controlled synthesis of high order main-chain mechanically interlocked polymers. This tutorial review focuses (i) on the development of DCC-namely, the formation of dynamic imine bonds-used in conjunction with template-directed protocols to afford a variety of mechanically interlocked molecules (MIMs) and ultimately (ii) on the synthesis of highly ordered poly[n]rotaxanes with high conversion efficiencies.

Easy access to a family of polymer catalysts from modular star polymers.

We report a versatile and scalable synthesis of a water-dispersible modular star polymer platform with an enzyme-inspired hydrophobic interior. The cores of the stars can be functionalized at will, independently from the modification of the polymer structure. We explored the use of this material for the creation of a local hydrophobic solvent environment in water and for site isolation of incompatible catalytic entities.