Tandem High-Pressure Crystallography-Optical Spectroscopy Unpacks Noncovalent Interactions of Piezochromic Fluorescent Molecular Rotors.

To develop luminescent molecular materials with predictable and stimuli-responsive emission, it is necessary to correlate changes in their geometries, packing structures, and noncovalent interactions with the associated changes in their optical properties. Here, we demonstrate that high-pressure single-crystal X-ray diffraction can be combined with high-pressure UV-visible absorption and fluorescence emission spectroscopies to elucidate how subtle changes in structure influence optical outputs. A piezochromic aggregation-induced emitter, sym-heptaphenylcycloheptatriene (Ph7C7H), displays bathochromic shifts in its absorption and emission spectra at high pressure. Parallel X-ray measurements identify the pressure-induced changes in specific phenyl-phenyl interactions responsible for the piezochromism. Pairs of phenyl rings from neighboring molecules approach the geometry of a stable benzene dimer, while conformational changes alter intramolecular phenyl-phenyl interactions correlated with a relaxed excited state. This tandem crystallographic and spectroscopic analysis provides insights into how subtle structural changes relate to the photophysical properties of Ph7C7H and could be applied to a library of similar compounds to provide general structure-property relationships in fluorescent organic molecules with rotor-like geometries.

Aggregation-Induced Emission (AIE), Life and Health.

Light has profoundly impacted modern medicine and healthcare, with numerous luminescent agents and imaging techniques currently being used to assess health and treat diseases. As an emerging concept in luminescence, aggregation-induced emission (AIE) has shown great potential in biological applications due to its advantages in terms of brightness, biocompatibility, photostability, and positive correlation with concentration. This review provides a comprehensive summary of AIE luminogens applied in imaging of biological structure and dynamic physiological processes, disease diagnosis and treatment, and detection and monitoring of specific analytes, followed by representative works. Discussions on critical issues and perspectives on future directions are also included. This review aims to stimulate the interest of researchers from different fields, including chemistry, biology, materials science, medicine, etc., thus promoting the development of AIE in the fields of life and health.

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.

Control of dynamic sp3-C stereochemistry.

Stereogenic sp3-hybridized carbon centres are fundamental building blocks of chiral molecules. Unlike dynamic stereogenic motifs, such as sp3-nitrogen centres or atropisomeric biaryls, sp3-carbon centres are usually fixed, requiring intermolecular reactions to undergo configurational changes. Here we report the internal enantiomerization of fluxional carbon cages and the consequences of their adaptive configurations for the transmission of stereochemical information. The sp3-carbon stereochemistry of the rigid tricyclic cages is inverted through strain-assisted Cope rearrangements, emulating the low-barrier configurational dynamics typical for sp3-nitrogen inversion or conformational isomerism. This dynamic enantiomerization can be stopped, restarted or slowed by external reagents, while the configuration of the cage is controlled by neighbouring, fixed stereogenic centres. As part of a phosphoramidite-olefin ligand, the fluxional cage acts as a conduit to transmit stereochemical information from the ligand while also transferring its dynamic properties to chiral-at-metal coordination environments, influencing catalysis, ion pairing and ligand exchange energetics.

Extended Conjugation Attenuates the Quenching of Aggregation-Induced Emitters by Photocyclization Pathways.

Herein, we expose how the antagonistic relationship between solid-state luminescence and photocyclization of oligoaryl alkene chromophores is modulated by the conjugation length of their alkenyl backbones. Heptaaryl cycloheptatriene molecular rotors exhibit aggregation-induced emission characteristics. We show that their emission is turned off upon breaking the conjugation of the cycloheptatriene by epoxide formation. While this modification is deleterious to photoluminescence, it enables formation of extended polycyclic frameworks by Mallory reactions. We exploit this dichotomy (i) to manipulate emission properties in a controlled manner and (ii) as a synthetic tool to link together pairs of phenyl rings in a specific sequence. This method to alter the tendency of oligoaryl alkenes to undergo photocyclization can inform the design of solid-state emitters that avoid this quenching mechanism, while also allowing selective cyclization in syntheses of polycyclic aromatic hydrocarbons.

Control of Porphyrin Planarity and Aggregation by Covalent Capping: Bissilyloxy Porphyrin Silanes.

Porphyrins are cornerstone functional materials that are useful in a wide variety of settings, ranging from molecular electronics to biology and medicine. Their applications are often hindered, however, by poor solubilities that result from their extended, solvophobic aromatic surfaces. Attempts to counteract this problem by functionalizing their peripheries have been met with only limited success. Here, we demonstrate a versatile strategy to tune the physical and electronic properties of porphyrins using an axial functionalization approach. Porphyrin silanes (PorSils) and bissilyloxy PorSils (SOPS) are prepared from porphyrins by operationally simple κ4N-silylation protocols, introducing bulky silyloxy "caps" that are central and perpendicular to the planar porphyrin. While porphyrins typically form either J- or H-aggregates, SOPS do not self-associate in the same manner: the silyloxy axial substituents dramatically improve the solubility by inhibiting aggregation. Moreover, axial porphyrin functionalization offers convenient handles through which optical, electronic, and structural properties of the porphyrin core can be modulated. We observe that the identity of the silyloxy substituent impacts the degree of planarity of the porphyrin in the solid state as well as the redox potentials.

Aggregate Science: From Structures to Properties.

Molecular science entails the study of structures and properties of materials at the level of single molecules or small interacting complexes of molecules. Moving beyond single molecules and well-defined complexes, aggregates (i.e., irregular clusters of many molecules) serve as a particularly useful form of materials that often display modified or wholly new properties compared to their molecular components. Some unique structures and phenomena such as polymorphic aggregates, aggregation-induced symmetry breaking, and cluster excitons are only identified in aggregates, as a few examples of their exotic features. Here, by virtue of the flourishing research on aggregation-induced emission, the concept of "aggregate science" is put forward to fill the gaps between molecules and aggregates. Structures and properties on the aggregate scale are also systematically summarized. The structure-property relationships established for aggregates are expected to contribute to new materials and technological development. Ultimately, aggregate science may become an interdisciplinary research field and serves as a general platform for academic research.

Shapeshifting molecules: the story so far and the shape of things to come.

Shapeshifting molecules exhibit rapid constitutional dynamics while remaining stable, isolable molecules, making them promising artificial scaffolds from which to explore complex biological systems and create new functional materials. However, their structural complexity presents challenges for designing their syntheses and understanding their equilibria. This minireview showcases (1) recent applications of highly dynamic shapeshifting molecules in sensing and distinguishing complex small molecules and (2) detailed insights into the adaptation of tractable bistable systems to changes in their local environment. The current status of this field is summarised and its future prospects are discussed.

Modulation of charge transfer by N-alkylation to control photoluminescence energy and quantum yield.

Charge transfer in organic fluorophores is a fundamental photophysical process that can be either beneficial, e.g., facilitating thermally activated delayed fluorescence, or detrimental, e.g., mediating emission quenching. N-Alkylation is shown to provide straightforward synthetic control of the charge transfer, emission energy and quantum yield of amine chromophores. We demonstrate this concept using quinine as a model. N-Alkylation causes changes in its emission that mirror those caused by changes in pH (i.e., protonation). Unlike protonation, however, alkylation of quinine's two N sites is performed in a stepwise manner to give kinetically stable species. This kinetic stability allows us to isolate and characterize an N-alkylated analogue of an 'unnatural' protonation state that is quaternized selectively at the less basic site, which is inaccessible using acid. These materials expose (i) the through-space charge-transfer excited state of quinine and (ii) the associated loss pathway, while (iii) developing a simple salt that outperforms quinine sulfate as a quantum yield standard. This N-alkylation approach can be applied broadly in the discovery of emissive materials by tuning charge-transfer states.

Persistent Dimer Emission in Thermally Activated Delayed Fluorescence Materials.

We expose significant changes in the emission color of carbazole-based thermally activated delayed fluorescence (TADF) emitters that arise from the presence of persistent dimer states in thin films and organic light-emitting diodes (OLEDs). Direct photoexcitation of this dimer state in 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) reveals the significant influence of dimer species on the color purity of its photoluminescence and electroluminescence. The dimer species is sensitive to the sample preparation method, and its enduring presence contributes to the widely reported concentration-mediated red shift in the photoluminescence and electroluminescence of evaporated thin films. This discovery has implications on the usability of these, and similar, molecules for OLEDs and explains disparate electroluminescence spectra presented in the literature for these compounds. The dimerization-controlled changes observed in the TADF process and photoluminescence efficiency mean that careful consideration of dimer states is imperative in the design of future TADF emitters and the interpretation of previously reported studies of carbazole-based TADF materials.

Shape-selective crystallisation of fluxional carbon cages.

Dynamic covalent rearrangements of fluxional carbon cages, such as bullvalenes and barbaralanes, impart 'shapeshifting' molecular properties. Here, a series of five barbaralanes each interconvert dynamically between two constitutional isomers in solution, but resolve to single isomers upon crystallisation. Unexpectedly, the minor solution-phase isomers are resolved in two instances. Through dynamic NMR, crystallographic and DFT analyses, we show that the isomer observed in the solid state is not a direct consequence of the equilibrium distribution in solution or any specific noncovalent interactions. Rather, the dynamic preferential crystallisation is dictated by differences in molecular size and shape.

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.

Triply Threaded [4]Rotaxanes.

[4]Rotaxanes featuring three axles threaded through a single ring have been prepared through active metal template synthesis. Nickel-catalyzed sp(3)-sp(3) homocouplings of alkyl bromide "half-threads" through 37- and 38-membered 2,2':6',2″-terpyridyl macrocycles generate triply threaded [4]rotaxanes in up to 11% yield. An analogous 39-membered macrocycle produced no rotaxane products under similar conditions. The constitutions of the [4]rotaxanes were determined by NMR spectroscopy and mass spectrometry. Doubly threaded [3]rotaxanes were also obtained from the reactions but no [2]rotaxanes were isolated, suggesting that upon demetalation the axle of a singly threaded rotaxane can slip through a macrocycle that is sufficiently large to accommodate three threads.

Hydroacenes Made Easy by Gold(I) Catalysis.

A novel strategy for the synthesis of partially saturated acene derivatives has been developed based on a Au(I) -catalyzed cyclization of 1,7-enynes. This method provides straightforward access to stable polycyclic products featuring the backbone of the acene series, up to nonacene.

Influence of Constitution and Charge on Radical Pairing Interactions in Tris-radical Tricationic Complexes.

The results of a systematic investigation of trisradical tricationic complexes formed between cyclobis(paraquat-p-phenylene) bisradical dicationic (CBPQT(2(•+))) rings and a series of 18 dumbbells, containing centrally located 4,4'-bipyridinium radical cationic (BIPY(•+)) units within oligomethylene chains terminated for the most part by charged 3,5-dimethylpyridinium (PY(+)) and/or neutral 3,5-dimethylphenyl (PH) groups, are reported. The complexes were obtained by treating equimolar amounts of the CBPQT(4+) ring and the dumbbells containing BIPY(2+) units with zinc dust in acetonitrile solutions. Whereas UV-Vis-NIR spectra revealed absorption bands centered on ca. 1100 nm with quite different intensities for the 1:1 complexes depending on the constitutions and charges on the dumbbells, titration experiments showed that the association constants (Ka) for complex formation vary over a wide range, from 800 M(-1) for the weakest to 180 000 M(-1) for the strongest. While Coulombic repulsions emanating from PY(+) groups located at the ends of some of the dumbbells undoubtedly contribute to the destabilization of the trisradical tricationic complexes, solid-state superstructures support the contention that those dumbbells with neutral PH groups at the ends of flexible and appropriately constituted links to the BIPY(•+) units stand to gain some additional stabilization from C-H···π interactions between the CBPQT(2(•+)) rings and the PH termini on the dumbbells. The findings reported in this Article demonstrate how structural changes implemented remotely from the BIPY(•+) units influence their non-covalent bonding interactions with CBPQT(2(•+)) rings. Different secondary effects (Coulombic repulsions versus C-H···π interactions) are uncovered, and their contributions to both binding strengths associated with trisradical interactions and the kinetics of associations and dissociations are discussed at some length, supported by extensive DFT calculations at the M06-D3 level. A fundamental understanding of molecular recognition in radical complexes has relevance when it comes to the design and synthesis of non-equilibrium systems.

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.

Design and Synthesis of Nonequilibrium Systems.

The active transport of ions and molecules across cell membranes is essential to creating the concentration gradients that sustain life in all living organisms, be they bacteria, fungi, plants, animals or Homo sapiens. Nature uses active transport everywhere for everything. Molecular biologists have long been attracted to the study of active transport and continue to this day to investigate and elucidate the tertiary structures of the complex motor proteins that sustain it, while physicists, interested in nonequilibrium statistical mechanics, have developed theoretical models to describe the driven ratcheting motions that are crucial to its function. The increasingly detailed understanding that contemporary science has acquired relating to active transport, however, has yet to lead to the design and construction of artificial molecular motors capable of employing ratchet-driven motions that can also perform work against concentration gradients. Mechanically interlocked molecules (MIMs) in the form of pseudo- and semirotaxanes are showing some encouraging signs in meeting these goals. This review summarizes recent progress in making artificial molecular motors that can perform work by "pumping" tetracationic rings into high-energy states. The launching pad is a bistable [2]rotaxane whose dumbbell component contains two electron-donating recognition sites, one, a tetrathiafulvalene (TTF) unit, which interacts more strongly with the ring component, cyclobis(paraquat-p-phenylene) (CBPQT(4+)), containing two electron-accepting bipyridinium units, than does the other 1,5-dioxynaphthalene (DNP) unit. Switching can be induced electrochemically by oxidizing the TTF unit to a TTF(•+) radical cation, whereupon Coulombic repulsion takes care of moving the ring to the DNP unit. Reduction of the radical cation resets the switch. Molecular switches operate at, or close to, equilibrium. Any work done during one switching event is undone during the reset. Molecular motors, on the other hand, rely on a flux of energy, and a ratchet mechanism to make periodic changes to the potential energy surface of a system in order to move molecules uphill to higher energy states. Forging a path from molecular switches to motors involved designing a molecular pump prototype. An asymmetric dumbbell with a 2-isopropylphenyl (neutral) end and a 3,5-dimethylpyridinium (charged) end with a DNP recognition site to entice CBPQT(4+) rings out of solution exhibits relative unidirectional movement of the rings with respect to the dumbbell. Redox chemistry does the trick. During the oxidative cycle, the rings enter the dumbbell by passing over the neutral end onto the recognition site; in the reduction cycle, much of the recognition is lost and the rings find their way back into solution by leaving the dumbbell from the charged end. This on-one-end, off-the-other process can be repeated over and over again using light as the energy source in the presence of a photosensitizer and a compound that shuttles electrons back and forth. Although this prototype demonstrates ratchet-driven translational motion, no work is done. A ring enters the dumbbell from one end and leaves from the other end. Another deficiency of the prototype is the fact that, although the recognition site is muted on reduction, it retains some attraction for the ring. What if the recognition site was attractive initially and then became repulsive? This question was answered by turning to radical chemistry and employing the known stabilization behavior of a bipyridinium radical cation and the bisradical dication, generated on reduction of the CBPQT(4+) ring, to pluck rings out of solution and thread them over the charged end of the pump portion of a semidumbbell. On subsequent oxidation, the pump is primed and the rings pass through a one-way door, given a little thermal energy, onto a collecting-chain where they find themselves accumulating where they would rather not be present. In this manner, an artificial molecular pump mimics the pumping machinery commonplace in biological systems. Looking beyond this state-of-the-art artificial molecular pump, we discuss, from a theoretical standpoint, the measures that would need to be taken in order to render its operation autonomous.

An artificial molecular pump.

Carrier proteins consume fuel in order to pump ions or molecules across cell membranes, creating concentration gradients. Their control over diffusion pathways, effected entirely through noncovalent bonding interactions, has inspired chemists to devise artificial systems that mimic their function. Here, we report a wholly artificial compound that acts on small molecules to create a gradient in their local concentration. It does so by using redox energy and precisely organized noncovalent bonding interactions to pump positively charged rings from solution and ensnare them around an oligomethylene chain, as part of a kinetically trapped entanglement. A redox-active viologen unit at the heart of a dumbbell-shaped molecular pump plays a dual role, first attracting and then repelling the rings during redox cycling, thereby enacting a flashing energy ratchet mechanism with a minimalistic design. Our artificial molecular pump performs work repetitively for two cycles of operation and drives rings away from equilibrium toward a higher local concentration.

Tunable solid-state fluorescent materials for supramolecular encryption.

Tunable solid-state fluorescent materials are ideal for applications in security printing technologies. A document possesses a high level of security if its encrypted information can be authenticated without being decoded, while also being resistant to counterfeiting. Herein, we describe a heterorotaxane with tunable solid-state fluorescent emissions enabled through reversible manipulation of its aggregation by supramolecular encapsulation. The dynamic nature of this fluorescent material is based on a complex set of equilibria, whose fluorescence output depends non-linearly on the chemical inputs and the composition of the paper. By applying this system in fluorescent security inks, the information encoded in polychromic images can be protected in such a way that it is close to impossible to reverse engineer, as well as being easy to verify. This system constitutes a unique application of responsive complex equilibria in the form of a cryptographic algorithm that protects valuable information printed using tunable solid-state fluorescent materials.

Oxime ligation on the surface of mesoporous silica nanoparticles.

A versatile surface-functionalization strategy applicable to mesoporous silica nanoparticles, which could potentially serve as drug delivery vehicles, is described that makes use of alkoxyamine tethers on the surface of the nanoparticles. A wide variety of carbonyl compounds can be attached readily to these tethers under the mild conditions of oxime ether formation, simply by incubating the chemically modified mesoporous silica nanoparticles with aldehydes or ketones in water.