Cooperatively assembled liquid crystals enable temperature-controlled Förster resonance energy transfer

Balancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal–optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system. Indeed, FRET exhibits strong S-curve dependence as temperature sweeps through the liquid crystal phase transformation. Such thermochromic materials, suitable for dynamic thermo-optical sensing and modulation, are anticipated to unlock new and smart approaches for controlling and directing light in stimuli-responsive devices.

A temperature-sensitive Förster resonance energy transfer system was constructed using a highly emissive liquid crystal co-assembled with Nile red, enabling thermo-optical modulation for controlling and directing light in stimuli-responsive devices.     

Correlated motion and mechanical gearing in amphidynamic crystalline molecular machines

In this review we highlight the recent efforts towards the development of molecular gears with an emphasis on building molecular gears in the solid state and the role that molecular gearing and correlated motions may play in the function of crystalline molecular machines. We discuss current molecular and crystal engineering strategies, challenges associated with engineering correlated motion in crystals, and outline experimental and theoretical tools to explore gearing dynamics while highlighting key advances made to date.

Here we highlight recent efforts towards the development of molecular gears in the solid state and the role that molecular gearing and correlated motions may play in the function of crystalline molecular machines.     

Supramolecular chemistry under mechanochemical conditions: a small molecule template generated and integrated into a molecular-to-supramolecular and back-to-molecular cascade reaction

We describe the integration of a small-molecule hydrogen-bond-donor template into a cascade reaction that is comprised of a combination of molecular and supramolecular events. The cascade is performed mechanochemically and in the presence of μL amounts of water. The small-molecule template is generated (molecular) using water-assisted vortex grinding and is then used to assemble an alkene (supramolecular) to undergo an intermolecular [2 + 2] photodimerization reaction (molecular). The chemical cascade results in a cyclobutane photoproduct that we show serves as a building block of a hydrogen-bonded network with a topology that conforms to T-silica. Remarkably, the molecular–supramolecular–molecular chemical cascade occurs stepwise and entirely regioselectively within the continuous mechanochemical conditions employed.

Mechanochemistry is applied to molecular and supramolecular chemistry to support a template-directed photochemical reaction.     

Designing naphthopyran mechanophores with tunable mechanochromic behavior

Mechanochromic molecular force probes conveniently report on stress and strain in polymeric materials through straightforward visual cues. We capitalize on the versatility of the naphthopyran framework to design a series of mechanochromic mechanophores that exhibit highly tunable color and fading kinetics after mechanochemical activation. Structurally diverse naphthopyran crosslinkers are synthesized and covalently incorporated into silicone elastomers, where the mechanochemical ring–opening reactions are achieved under tension to generate the merocyanine dyes. Strategic structural modifications to the naphthopyran mechanophore scaffold produce dramatic differences in the color and thermal electrocyclization behavior of the corresponding merocyanine dyes. The color of the merocyanines varies from orange-yellow to purple upon the introduction of an electron donating pyrrolidine substituent, while the rate of thermal electrocyclization is controlled through electronic and steric factors, enabling access to derivatives that display both fast-fading and persistent coloration after mechanical activation and subsequent stress relaxation. In addition to identifying key structure–property relationships for tuning the behavior of the naphthopyran mechanophore, the modularity of the naphthopyran platform is demonstrated by leveraging blends of structurally distinct mechanophores to create materials with desirable multicolor mechanochromic and complex stimuli-responsive behavior, expanding the scope and accessibility of force-responsive materials for applications such as multimodal sensing.

Structure–activity relationships for strategic substitution of the naphthopyran mechanophore scaffold enable polymeric materials with tunable mechanochromic behavior.     

A clustering-triggered emission strategy for tunable multicolor persistent phosphorescence

A clustering-triggered emission (CTE) strategy, namely the formation of heterogeneous clustered chromophores and conformation rigidification, for achieving tunable multicolor phosphorescence in single-component compounds is proposed. Non-conventional luminophores comprising just oxygen functionalities and free of π-bonding, i.e., d-(+)-xylose (d-Xyl), pentaerythritol (PER), d-fructose (d-Fru) and d-galactose (d-Gal), were adopted as a simple model system with an explicit structure and molecular packing to address the hypothesis. Their concentrated solutions and crystals at 77 K or under ambient conditions demonstrate remarkable multicolor phosphorescence afterglows in response to varying excitation wavelengths, because of the formation of diverse oxygen clusters with sufficiently rigid conformations. The intra- and inter-molecular O⋯O interactions were definitely illustrated by both single crystal structure analysis and theoretical calculations. These findings shed new light on the origin and simple achievement of tunable multicolor phosphorescence in single-component pure organics, and in turn, have strong implications for the emission mechanism of non-conventional luminophores.

A clustering-triggered emission strategy is proposed to readily realize tunable multicolor afterglows in single-component pure organic compounds.     

Modulated self-assembly of metal–organic frameworks

Exercising fine control over the synthesis of metal–organic frameworks (MOFs) is key to ensuring reproducibility of physical properties such as crystallinity, particle size, morphology, porosity, defectivity, and surface chemistry. The principle of modulated self-assembly – incorporation of modulator molecules into synthetic mixtures – has emerged as the primary means to this end. This perspective article will detail the development of modulated synthesis, focusing primarily on coordination modulation, from a technique initially intended to cap the growth of MOF crystals to one that is now used regularly to enhance crystallinity, control particle size, induce defectivity and select specific phases. The various mechanistic driving forces will be discussed, as well as the influence of modulation on physical properties and how this can facilitate potential applications. Modulation is also increasingly being used to exert kinetic control over self-assembly; examples of phase selection and the development of new protocols to induce this will be provided. Finally, the application of modulated self-assembly to alternative materials will be discussed, and future perspectives on the area given.

This Perspective gives an overview of the modulated self-assembly of MOFs – incorporating additives and alternative precursors into syntheses – focusing on its varying influences on crystallization mechanisms, physical properties, and applications.     

Hierarchical two-dimensional molecular assembly through dynamic combination of conformational states at the liquid/solid interface

Self-sorting of multiple building blocks for correctly positioning molecules through orthogonal recognition is a promising strategy for construction of a hierarchical self-assembled molecular network (SAMN) on a surface. Herein we report that a trigonal molecule, dehydrobenzo[12]annulene (DBA) derivative having three tetradecyloxy chains and three hydroxy groups in an alternating manner, forms hierarchical triangular clusters of different sizes ranging from 2.4 to 16.4 nm, consisting of 3 to 78 molecules, respectively, at the liquid/graphite interface. The key is the dynamic combination of three different conformational states, which is solvent and concentration dependent. The present knowledge extends design strategies for production of sophisticated hierarchical SAMNs using a single component at the liquid/solid interface.

Self-sorting of multiple building blocks for correctly positioning molecules through orthogonal recognition is a promising strategy for construction of a hierarchical self-assembled molecular network (SAMN) on a surface.     

Regio- and diastereoselective dearomatizations of N-alkyl activated azaarenes: the maximization of the reactive sites

An unprecedented base-promoted multi-component one-pot dearomatization of N-alkyl activated azaarenes was developed, which enabled the synthesis of complex and diverse bridged cyclic polycycles with multiple stereocenters in a highly regio- and diastereoselective manner. Besides, we realized the step-controlled dearomative bi- and trifunctionalization of quinolinium salts. These transformations not only achieved the maximization of the reaction sites of pyridinium, quinolinium and isoquinolinium salts to enhance structural complexity and diversity, but also opened up a new reaction mode of these N-activated azaarenes. A unique feature of this strategy is the use of easily accessible and bench-stable N-alkyl activated azaarenes to provide maximum reactive sites for dearomative cascade cyclizations. In addition, the salient characteristics including high synthetic efficiency, short reaction time, mild conditions and simple operation made this strategy particularly attractive.

An unprecedented base-promoted multi-component one-pot dearomatization of N-alkyl activated azaarenes was developed to construct complex and diverse bridged cyclic polycycles with multiple stereocenters in a highly regio- and diastereoselective manner.     

Sustainable and rapid preparation of nanosized Fe/Ni-pentlandite particles by mechanochemistry

In recent years, metal-rich sulfides of the pentlandite type (M₉S₈) have attracted considerable attention for energy storage applications. However, common synthetic routes towards pentlandites either involve energy intensive high temperature procedures or solvothermal methods with specialized precursors and non-sustainable organic solvents. Herein, we demonstrate that ball milling is a simple and efficient method to synthesize nanosized bimetallic pentlandite particles (Fe_4.5Ni_4.5S₈, Pn) with an average size of ca. 250 nm in a single synthetic step from elemental- or sulfidic mixtures. We herein highlight the effects of the milling ball quantity, precursor types and milling time on the product quality. Along this line, Raman spectroscopy as well as temperature/pressure monitoring during the milling processes provide valuable insights into mechanistic differences between the mechanochemical Pn-formation. By employing the obtained Pn-nanosized particles as cathodic electrocatalysts for water splitting in a zero-gap PEM electrolyzer we provide a comprehensive path for a potential sustainable future process involving non-noble metal catalysts.

A sustainable and rapid mechanochemical method for the preparation of bimetallic nanosized pentlandite particles as cathode material is developed and tested within zero-gap PEM cells.     

Sustainable existence of solid mercury (Hg) nanoparticles at room temperature and their applications

Although liquid mercury (Hg) has been known since antiquity, the formation of stable solid nano forms of Hg at room temperature has not been reported so far. Here, for the first time, we report a simple sonochemical route to obtain solid mercury nanoparticles, stabilized by reduced graphene oxide at ambient conditions. The as-formed solid Hg nanoparticles were found to exhibit remarkable rhombohedral morphology and crystallinity at room temperature. Extensive characterization using various physicochemical techniques revealed the unique properties of the solid nanoparticles of Hg compared to its bulk liquid metal phase. Furthermore, the solid nature of the Hg nanoparticles was studied electrochemically, revealing distinctive properties. We believe that solid Hg nanoparticles have the potential for important applications in the fields of electroanalytical chemistry and electrocatalysis.

Formation of the stable solid mercury nanoparticles by acoustic cavitation and their electrochemical activity compared to its bulk liquid metal.     

Using steric hindrance to manipulate and stabilize metal halide perovskites for optoelectronics

The chemical instability of metal halide perovskite materials can be ascribed to their unique properties of softness, in which the chemical bonding between metal halide octahedral frameworks and cations is the weak ionic and hydrogen bonding as in most perovskite structures. Therefore, various strategies have been developed to stabilize the cations and metal halide frameworks, which include incorporating additives, developing two-dimensional perovskites and perovskite nanocrystals, etc. Recently, the important role of utilizing steric hindrance for stabilizing and passivating perovskites has been demonstrated. In this perspective, we summarize the applications of steric hindrance in manipulating and stabilizing perovskites. We will also discuss how steric hindrance influences the fundamental kinetics of perovskite crystallization and film formation processes. The similarities and differences of the steric hindrance between perovskite solar cells and perovskite light emission diodes are also discussed. In all, utilizing steric hindrance is a promising strategy to manipulate and stabilize metal halide perovskites for optoelectronics.

Manipulation on steric hindrance can influence the fundamental kinetics of perovskite crystallization and film formation, therefore stabilizing and passivating perovskite structures, and promoting the commercialization of stable perovskite devices.     

Reference-free NOE NMR analysis

Nuclear Overhauser Effect (NOE) methods in NMR are an important tool for 3D structural analysis of small molecules. Quantitative NOE methods conventionally rely on reference distances, known distances that have to be spectrally separated and are not always available. Here we present a new method for evaluation and 3D structure selection that does not require a reference distance, instead utilizing structures optimized by molecular mechanics, enabling NOE evaluation even on molecules without suitable reference groups.

A quantitative Nuclear Overhauser Effect (NOE) analysis approach that avoids the use of and internal reference distance to perform molecular configuration selection.     

Singlet fission in a hexacene dimer: energetics dictate dynamics

Singlet fission (SF) is an exciton multiplication process with the potential to raise the efficiency limit of single junction solar cells from 33% to up to 45%. Most chromophores generally undergo SF as solid-state crystals. However, when such molecules are covalently coupled, the dimers can be used as model systems to study fundamental photophysical dynamics where a singlet exciton splits into two triplet excitons within individual molecules. Here we report the synthesis and photophysical characterization of singlet fission of a hexacene dimer. Comparing the hexacene dimer to analogous tetracene and pentacene dimers reveals that excess exoergicity slows down singlet fission, similar to what is observed in molecular crystals. Conversely, the lower triplet energy of hexacene results in an increase in the rate of triplet pair recombination, following the energy gap law for radiationless transitions. These results point to design rules for singlet fission chromophores: the energy gap between singlet and triplet pair should be minimal, and the gap between triplet pair and ground state should be large.

We report the synthesis and photophysical characterization of highly exoergic singlet fission in a hexacene dimer revealing exciton dynamics that follow the energy gap law.     

A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals

Organic radicals are an emerging class of luminophores possessing multiplet spin states and potentially showing spin-luminescence correlated properties. We investigated the mechanism of recently reported magnetic field sensitivity in the emission of a photostable luminescent radical, (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM) doped into host αH-PyBTM molecular crystals. The magnetic field (0–14 T), temperature (4.2–20 K), and the doping concentration (0.1, 4, 10, and 22 wt%) dependence on the time-resolved emission were examined by measuring emission decays of the monomer and excimer. Quantum mechanical simulations on the decay curves disclosed the role of the magnetic field; it dominantly affects the spin sublevel population of radical dimers in the ground states. This situation is distinctly different from that in conventional closed-shell luminophores, where the magnetic field modulates their excited-state spin multiplicity. Namely, the spin degree of freedom of ground-state open-shell molecules is a new key for achieving magnetic-field-controlled molecular photofunctions.

We investigated the mechanism of the magnetic field effect (MFE) on the emission of a luminescent radical doped into host crystals. It was revealed that the spin sublevel population of radical dimers in the ground states is the key that governs the MFE.     

A review on machine learning algorithms for the ionic liquid chemical space

There are thousands of papers published every year investigating the properties and possible applications of ionic liquids. Industrial use of these exceptional fluids requires adequate understanding of their physical properties, in order to create the ionic liquid that will optimally suit the application. Computational property prediction arose from the urgent need to minimise the time and cost that would be required to experimentally test different combinations of ions. This review discusses the use of machine learning algorithms as property prediction tools for ionic liquids (either as standalone methods or in conjunction with molecular dynamics simulations), presents common problems of training datasets and proposes ways that could lead to more accurate and efficient models.

In this review article, the authors discuss the use of machine learning algorithms as tools for the prediction of physical and chemical properties of ionic liquids.     

Coacervate formation studied by explicit solvent coarse-grain molecular dynamics with the Martini model

Complex coacervates are liquid–liquid phase separated systems, typically containing oppositely charged polyelectrolytes. They are widely studied for their functional properties as well as their potential involvement in cellular compartmentalization as biomolecular condensates. Diffusion and partitioning of solutes into a coacervate phase are important to address because their highly dynamic nature is one of their most important functional characteristics in real-world systems, but are difficult to study experimentally or even theoretically without an explicit representation of every molecule in the system. Here, we present an explicit-solvent, molecular dynamics coarse-grain model of complex coacervates, based on the Martini 3.0 force field. We demonstrate the accuracy of the model by reproducing the salt dependent coacervation of poly-lysine and poly-glutamate systems, and show the potential of the model by simulating the partitioning of ions and small nucleotides between the condensate and surrounding solvent phase. Our model paves the way for simulating coacervates and biomolecular condensates in a wide range of conditions, with near-atomic resolution.

Martini 3 force field can capture the experimental trends of complex coacervates and can be extended to gain physical insight on the mechanisms that drive the formation of LLPS.     

Non-stackable molecules assemble into porous crystals displaying concerted cavity-changing motions

With small molecules, it is not easy to create large void spaces. Flat aromatics stack tightly, while flexible chains fold to fill the cavities. As an intuitive design to make open channels inside molecularly constructed solids, we employed propeller-shaped bicyclic triazoles to prepare a series of aromatic-rich three-dimensional (3D) building blocks. This modular approach has no previous example, but is readily applicable to build linear, bent, and branched arrays of non-stackable architectural motifs from existing flat aromatics by single-pot reactions. A letter H-shaped molecule thus prepared self-assembles into porous crystals, the highly unusual stepwise gas sorption behaviour of which prompted in-depth studies. A combination of single-crystal and powder X-ray diffraction analysis revealed multiple polymorphs, and sterically allowed pathways for their reversible interconversions that open and close the pores in response to external stimuli.

Like non-collapsible open voids within stacks of steel H-beams, a non-covalent assembly of three-dimensional aromatics produces porous crystals. Concerted motions of the molecular H-beams open and close the cavities in response to external stimuli.     

Accelerated reactions of amines with carbon dioxide driven by superacid at the microdroplet interface

Microdroplets display distinctive interfacial chemistry, manifested as accelerated reactions relative to those observed for the same reagents in bulk. Carbon dioxide undergoes C–N bond formation reactions with amines at the interface of droplets to form carbamic acids. Electrospray ionization mass spectrometry displays the reaction products in the form of the protonated and deprotonated carbamic acid. Electrosonic spray ionization (ESSI) utilizing carbon dioxide as nebulization gas, confines reaction to the gas–liquid interface where it proceeds much faster than in the bulk. Intriguingly, trace amounts of water accelerate the reaction, presumably by formation of superacid or superbase at the water interface. The suggested mechanism of protonation of CO₂ followed by nucleophilic attack by the amine is analogous to that previously advanced for imidazole formation from carboxylic acids and diamines.

Microdroplets display distinctive interfacial chemistry, manifested as accelerated reactions relative to those observed for the same reagents in bulk.     

Leveraging autocatalytic reactions for chemical domain image classification

Autocatalysis is fundamental to many biological processes, and kinetic models of autocatalytic reactions have mathematical forms similar to activation functions used in artificial neural networks. Inspired by these similarities, we use an autocatalytic reaction, the copper-catalyzed azide–alkyne cycloaddition, to perform digital image recognition tasks. Images are encoded in the concentration of a catalyst across an array of liquid samples, and the classification is performed with a sequence of automated fluid transfers. The outputs of the operations are monitored using UV-vis spectroscopy. The growing interest in molecular information storage suggests that methods for computing in chemistry will become increasingly important for querying and manipulating molecular memory.

Kinetic models of autocatalytic reactions have mathematical forms similar to activation functions used in artificial neural networks. Inspired by these similarities, we use a copper-catalyzed reaction to perform digital image recognition tasks.