A Dissipative Reaction Network Drives Transient Solid-Liquid and Liquid-Liquid Phase Cycling of Nanoparticles.

Transient states maintained by energy dissipation are an essential feature of dynamic systems where structures and functions are regulated by fluxes of energy and matter through chemical reaction networks. Perfected in biology, chemically fueled dissipative networks incorporating nanoscale components allow the unique properties of nanomaterials to be bestowed with spatiotemporal adaptability and chemical responsiveness. We report the transient dispersion of gold nanoparticles in water, powered by dissipation of a chemical fuel.

An electric molecular motor.

Macroscopic electric motors continue to have a large impact on almost every aspect of modern society. Consequently, the effort towards developing molecular motors that can be driven by electricity could not be more timely. Here we describe an electric molecular motor based on a [3]catenane, in which two cyclobis(paraquat-p-phenylene) (CBPQT) rings are powered by electricity in solution to circumrotate unidirectionally around a 50-membered loop.

A Molecular Replication Process Drives Supramolecular Polymerization.

Supramolecular polymers are materials in which the connections between monomers in the polymer main chain are non-covalent bonds. This area has seen rapid expansion in the last two decades and has been exploited in several applications. However, suitable contiguous hydrogen-bond arrays can be difficult to synthesize, placing some limitations on the deployment of supramolecular polymers.

Encoding Multiple Reactivity Modes within a Single Synthetic Replicator.

Establishing programmable and self-sustaining replication networks in pools of chemical reagents is a key challenge in systems chemistry. Self-replicating templates are formed from two constituent components with complementary recognition and reactive sites via a slow bimolecular pathway and a fast template-directed pathway. Here, we re-engineer one of the components of a synthetic replicator to encode an additional recognition function, permitting the assembly of a binary complex between the components that mediates replicator formation through a template-independent pathway, which achieves maximum rate acceleration at early time points in the replication process.

Single-Crystal Polycationic Polymers Obtained by Single-Crystal-to-Single-Crystal Photopolymerization.

The efficient preparation of single-crystalline ionic polymers and fundamental understanding of their structure-property relationships at the molecular level remains a challenge in chemistry and materials science. Here, we describe the single-crystal structure of a highly ordered polycationic polymer (polyelectrolyte) and its proton conductivity. The polyelectrolyte single crystals can be prepared on a gram-scale in quantitative yield, by taking advantage of an ultraviolet/sunlight-induced topochemical polymerization, from a tricationic monomer-a self-complementary building block possessing a preorganized conformation.

Combining Intra- and Intermolecular Charge Transfer with Polycationic Cyclophanes To Design 2D Tessellations.

A series of donor-acceptor (D-A) naphthalene-viologen-based cyclophanes of different shapes, sizes, and symmetries have been synthesized and characterized. Solution optical studies on these cyclophanes reveal the existence of photoinduced intramolecular charge transfer (CT) at 465 nm from naphthalene (D) to viologen (A) units, resulting in a conformational change in the viologen units and the emergence of an emission at 540 nm. The D-A cyclophanes with box-like and hexagon-like shapes offer an opportunity to control the arrangement within 2D layers where D-A interactions direct the superstructures.

Compositional Persistence in a Multicyclic Network of Synthetic Replicators.

The emergence of collections of simple chemical entities that create self-sustaining reaction networks, embedding replication and catalysis, is cited as a potential mechanism for the appearance on the early Earth of systems that satisfy minimal definitions of life. In this work, a functional reaction network that creates and maintains a set of privileged replicator structures through auto- and cross-catalyzed reaction cycles is created from the pairwise combinations of four reagents. We show that the addition of individual preformed templates to this network, representing instructions to synthesize a specific replicator, induces changes in the output composition of the system that represent a network-level response.

Two Synthetic Replicators Compete To Process a Dynamic Reagent Pool.

Complementary building blocks, comprising a set of four aromatic aldehydes and a set of four nucleophiles-three anilines and one hydroxylamine-combine through condensation reactions to afford a dynamic covalent library (DCL) consisting of the eight starting materials and 16 condensation products. One of the aldehydes and, consequently, all of the DCL members derived from this compound bear an amidopyridine recognition site. Exposure of this DCL to two maleimides, M and M, each equipped with a carboxylic acid recognition site, results in the formation of a series of products through irreversible 1,3-dipolar cycloaddition reactions with the four nitrones present in the DCL.

An Environmentally Responsive Reciprocal Replicating Network.

A reciprocal replication system is constructed from four building blocks, A, B, C, and D, which react in a pairwise manner through either a 1,3-dipolar cycloaddition or the condensation reaction between an amine and an aldehyde to create two templates, trans-T and T. These templates are equipped with complementary recognition sites-two carboxylic acids ( trans-T) or two 4,6-dimethylamidopyridines (T)-that enable each template to direct the formation of its complementary partner through two mutually reinforcing cross-catalytic pathways, in which the templates trans-T or T preorganize the appropriate building blocks within two catalytically active ternary complexes: [C•D• trans-T] and [A•B•T]. The template-directed processes within these complexes generate a heteroduplex [ trans-T•T], which is shown to possess significant stability through kinetic simulations and fitting.

Exploring the emergence of complexity using synthetic replicators.

A significant number of synthetic systems capable of replicating themselves or entities that are complementary to themselves have appeared in the last 30 years. Building on an understanding of the operation of synthetic replicators in isolation, this field has progressed to examples where catalytic relationships between replicators within the same network and the extant reaction conditions play a role in driving phenomena at the level of the whole system. Systems chemistry has played a pivotal role in the attempts to understand the origin of biological complexity by exploiting the power of synthetic chemistry, in conjunction with the molecular recognition toolkit pioneered by the field of supramolecular chemistry, thereby permitting the bottom-up engineering of increasingly complex reaction networks from simple building blocks.

Generating System-Level Responses from a Network of Simple Synthetic Replicators.

The creation of reaction networks capable of exhibiting responses that are properties of entire systems represents a significant challenge for the chemical sciences. The system-level behavior of a reaction network is linked intrinsically to its topology and the functional connections between its nodes. A simple network of chemical reactions constructed from four reagents, in which each reagent reacts with exactly two others, can exhibit up-regulation of two products even when only a single chemical reaction is addressed catalytically.

A Critical Cross-Catalytic Relationship Determines the Outcome of Competition in a Replicator Network.

A network of two synthetic replicators exhibits a critical unidirectional cross-catalytic relationship that directs competing replication processes. In this network, nitrone N bearing a 6-methylamidopyridine recognition site can participate in 1,3-dipolar cycloaddition reactions with two maleimides that differ in the relative position of their carboxylic acid recognition site: either para (M) or meta (M) relative to the maleimide ring. These cycloaddition reactions create replicators trans-T and trans-T.

pH controlled assembly of a self-complementary halogen-bonded dimer.

Phenols and their corresponding phenoxide anions can form halogen bonds with neutral iodotriazoles. The strength of these interactions depends critically on the protonation state of the oxygen atom - the interaction of the phenoxide anion is more than an order of magnitude stronger than the corresponding phenol. The assembly of a molecule bearing both an iodotriazole and a phenoxide anion into a self-complementary dimer, stabilised by two halogen bonds between the phenoxide anions and the neutral iodotriazoles has been demonstrated.

Neutral iodotriazoles as scaffolds for stable halogen-bonded assemblies in solution.

The halogen bond (XB) donor properties of neutral 1,4-diaryl-5-iodo-1,2,3-triazoles are explored using a combination of computational and experimental results and are shown to be competitive in halogen bonding efficiency with the classic pentafluoroiodobenzene XB donor. The SAr reactivity of these donors permits the facile assembly of an iodotriazole functionalised with a 3-oxypyridine XB acceptor, thus generating a molecular scaffold capable of undergoing dimerisation through the formation of two halogen bonds. The formation of this halogen-bonded dimer is demonstrated by H and DOSY NMR experiments and a plausible structure generated using DFT calculations.

Cooperative Binding in a Phosphine Oxide-Based Halogen Bonded Dimer Drives Supramolecular Oligomerization.

Triphenylphosphine oxide forms halogen-bonded (XB) complexes with pentafluoroiodobenzene and a 1,4-diaryl-5-iodotriazole. The stability of these complexes is assessed computationally and by P NMR spectroscopy in toluene-d solution, where both complexes are weakly associated. This knowledge is applied to the design and synthesis of two self-complementary phosphine oxide-iodotriazole hybrids that incorporate a phosphine oxide XB acceptor and a 1,4-diphenyl-5-iodotriazole XB donor within the same molecule.

Exploring the self-assembly and energy transfer of dynamic supramolecular iridium-porphyrin systems.

We present the first examples of dynamic supramolecular systems composed of cyclometalated Ir(iii) complexes of the form of [Ir(C^N)(N^N)]PF (where C^N is mesppy = 2-phenyl-4-mesitylpyridinato and dFmesppy = 2-(4,6-difluorophenyl)-4-mesitylpyridinato and N^N is 4,4':2',2'':4'',4'''-quaterpyridine, qpy) and zinc tetraphenylporphyrin (ZnTPP), assembled through non-covalent interactions between the distal pyridine moieties of the qpy ligand located on the iridium complex and the zinc of the ZnTPP. The assemblies have been comprehensively characterized by a series of analytical techniques (H NMR titration experiments, 2D COSY and HETCOR NMR spectra and low temperature H NMR spectroscopy) and the crystal structures have been elucidated by X-ray diffraction. The optoelectronic properties of the assemblies and the electronic interaction between the iridium and porphyrin chromophoric units have been explored with detailed photophysical measurements, supported by time-dependent density functional theory (TD-DFT) calculations.

A Synthetic Replicator Drives a Propagating Reaction-Diffusion Front.

A simple synthetic autocatalytic replicator is capable of establishing and driving the propagation of a reaction-diffusion front within a 50 μL syringe. This replicator templates its own synthesis through a 1,3-dipolar cycloaddition reaction between a nitrone component, equipped with a 9-ethynylanthracene optical tag, and a maleimide. Kinetic studies using NMR and UV-vis spectroscopies confirm that the replicator forms efficiently and with high diastereoselectivity, and this replication process brings about a dramatic change in optical properties of the sample-a change in the color of the fluorescence in the sample from yellow to blue.

Exploiting recognition-mediated assembly and reactivity in [2]rotaxane formation.

A small molecular reaction network exploits recognition-mediated reactive processes in order to drive the assembly and formation of both a self-replicating linear template (thread) and a [2]rotaxane, in which the linear template is encircled by a diamide macrocycle. Complementary recognition sites, placed at strategic positions on the reactive building blocks, drive these assembly and replication processes. Template-instructed experiments show that the thread is capable of efficient self-replication and that no cross-catalytic relationships exist between the thread and the [2]rotaxane.

A reactive nitrone-based organogel that self-assembles from its constituents in chloroform.

The reversible reaction of an aldehyde with a hydroxylamine affords a nitrone which is capable of forming a stiff gel with chloroform at concentrations as low as 0.20 wt% (6 mM). The gelator forms dynamically from its constituents and the gel assembly can be degraded in a controlled manner through a recognition-mediated reaction that targets the nitrone component of the gel network.

Probing the Limits of Selectivity in a Recognition-Mediated Reaction Network Embedded within a Dynamic Covalent Library.

Two recognition-mediated reaction processes operating through reactive binary complexes drive resolution of a 24-component dynamic covalent library, assembled from individual aldehydes and nucleophiles. The effectiveness of the library resolution and selective amplification of one recognition-enabled species over another is limited by the difference in the rates of the recognition-mediated reactive processes and the strength of the recognition processes employed in the dynamic system.

Orthogonal Recognition Processes Drive the Assembly and Replication of a [2]Rotaxane.

Within a small, interconnected reaction network, orthogonal recognition processes drive the assembly and replication of a [2]rotaxane. Rotaxane formation is governed by a central, hydrogen-bonding-mediated binding equilibrium between a macrocycle and a linear component, which associate to give a reactive pseudorotaxane. Both the pseudorotaxane and the linear component undergo irreversible, recognition-mediated 1,3-dipolar cycloaddition reactions with a stoppering maleimide group, forming rotaxane and thread, respectively.

A recognition-mediated reaction drives amplification within a dynamic library.

A single, appropriately designed, recognition event targets and transforms one of two reactive members of an exchanging pool of compounds through a recognition-mediated irreversible cycloaddition reaction, altering dramatically the final composition and kinetic behaviour of the dynamic library.

All-cis 1,2,3,4,5,6-hexafluorocyclohexane is a facially polarized cyclohexane.

The highest-energy stereoisomer of 1,2,3,4,5,6-hexafluorocyclohexane, in which all of the fluorines are 'up', is prepared in a 12-step protocol. The molecule adopts a classic chair conformation with alternate C-F bonds aligned triaxially, clustering three highly electronegative fluorine atoms in close proximity. This generates a cyclohexane with a high molecular dipole (μ = 6.

Regiodivergent Lewis base-promoted O- to C-carboxyl transfer of furanyl carbonates.

Triazolinylidenes promote γ-selective C-carboxylation (up to 99 : 1 regioselectivity) in the O- to C-carboxyl transfer of furanyl carbonates in contrast to DMAP that promotes preferential α-C-carboxylation with moderate regiocontrol (typically 60 : 40 regioselectivity). The generality of this process is described and a simple mechanistic and kinetic model postulated to account for the observed regioselectivity.