Rigid,biconical hydrogen-bonded dimers that strongly encapsulate cationic guests in solution and the solid state

The octol of a new rigid, tetraarylene-bridged cavitand was investigated for self-assembly behaviour in solution. ¹H and DOSY NMR spectroscopic experiments show that the cavitand readily dimerizes through an unusual seam of interdigitated hydrogen-bonds that is resistant to disruption by polar co-solvents. The well-defined cavity encapsulates small cationic guests, but not their neutral counterparts, restricting the conformation of sequestered tetraethylammonium in solution and the solid state.

A robust, dimeric capsule forms quantitatively in low-polarity solvents via a seam of 8 hydrogen bonds. The resulting electron-rich cavity selectively binds small organic cations over neutral counterparts.     

Converting molecular luminescence to ultralong room-temperature phosphorescence via the excited state modulation of sulfone-containing heteroaromatics

Manipulating the molecular orbital properties of excited states and the subsequent relaxation processes can greatly alter the emission behaviors of luminophores. Herein we report a vivid example of this, with luminescence conversion from thermally activated delayed fluorescence (TADF) to ultralong room-temperature phosphorescence (URTP) via a facile substituent effect on a rigid benzothiazino phenothiazine tetraoxide (BTPO) core. Pristine BTPO with multiple heteroatoms shows obvious intramolecular charge transfer (ICT) excited states with small exchange energy, featuring TADF. Via delicately functionalizing the BTPO core with peripheral moieties, the excited states of the BTPO derivatives become a hybridized local and charge transfer (HLCT) state in the S₁ state and a local excitation (LE) dominated HLCT state in the T₁ state, with enlarged energy bandgaps. Upon dispersion in a polymer matrix, the BTPO derivatives exhibit a persistent bright green afterglow with long lifetimes of up to 822 ms and decent quantum yields of up to 11.6%.

The decoration of a BTPO core results in a change in the luminescence nature from TADF to URTP. The phosphors in an amorphous PMMA matrix showed monomeric URTP with phosphorescence lifetimes of up to 822 ms and quantum yields of up to 11.6%.     

Room-temperature phosphorescence of a supercooled liquid: kinetic stabilisation by desymmetrisation

Achieving organic room-temperature phosphorescence (RTP) in a solvent-free liquid state is a challenging task because the liquid state provides a less rigid environment than the crystal. Here, we report that an unsymmetrical heteroaromatic 1,2-diketone forms an organic RTP liquid. This diketone exists as a kinetically stable supercooled liquid, which resists crystallisation even under pricking or shearing stresses, and remains as a liquid for several months. The unsymmetrical diketone core is flexible, with eight distinct conformers possible, which prevents nucleation and growth for the liquid–solid transition. Interestingly, the thermodynamically stable crystalline solid-state was non-emissive. Thus, the RTP of the diketone was found to be liquiefaction-induced. Single-crystal X-ray structure analysis revealed that the diminished RTP of the crystal is due to insufficient intermolecular interactions and restricted access to an emissive conformer. Our work demonstrates that flexible unsymmetrical skeletons are promising motifs for bistable liquid–solid molecular systems, which are useful for the further development of stimuli-responsive materials that use phase transitions.

Metal-free, single-component, unsymmetrical 1,2-diketone exhibits liquefaction-induced room-temperature phosphorescence. Desymmetrisation provides the supercooled liquid with notable kinetic stability and phase-dependent phosphorescence properties.     

Improving the intrinsic activity of electrocatalysts for sustainable energy conversion: where are we and where can we go?

As we are in the midst of a climate crisis, there is an urgent need to transition to the sustainable production of fuels and chemicals. A promising strategy towards this transition is to use renewable energy for the electrochemical conversion of abundant molecules present in the earth''s atmosphere such as H₂O, O₂, N₂ and CO₂, to synthetic fuels and chemicals. A cornerstone to this strategy is the development of earth abundant electrocatalysts with high intrinsic activity towards the desired products. In this perspective, we discuss the importance and challenges involved in the estimation of intrinsic activity both from the experimental and theoretical front. Through a thorough analysis of published data, we find that only modest improvements in intrinsic activity of electrocatalysts have been achieved in the past two decades which necessitates the need for a paradigm shift in electrocatalyst design. To this end, we highlight opportunities offered by tuning three components of the electrochemical environment: cations, buffering anions and the electrolyte pH. These components can significantly alter catalytic activity as demonstrated using several examples, and bring us a step closer towards complete system level optimization of electrochemical routes to sustainable energy conversion.

We evaluate the improvements over the past two decades in intrinsic activity of electrocatalysts for sustainable energy conversion, and highlight opportunities from tuning the electrolyte.     

Shedding light on predicting and controlling emission chromaticity in multicomponent photoluminescent systems

Predictable colour tuning in multicomponent photoluminescent (PL) systems is achieved using mixtures of simultaneously emitting organic molecules. By mitigating the potential for energy transfer through the control of concentration, the resulting emission chromaticity of five dichromic PL systems is approximated as a linear combination of the emitting components and their corresponding brightness (χ_i, ϕ_i, and I_ex,i). Despite being limited to dilute solutions (10⁻⁶ M), colour tuning within these systems was controlled by (1) varying the composition of the components and (2) exploiting the differences in the components'' excitation intensities at common wavelengths. Using this approach, white light emission (WLE) was realized using a pre-determined mixture of red, green, and blue emitting organic molecules. Based on these results, materials and devices with built-in or programmable emission colour can be achieved, including highly sought-after WLE.

Predictable colour tuning in multicomponent photoluminescent (PL) systems is achieved using mixtures of simultaneously emitting organic molecules.     

Cyclic monoterpenes trapped in a polyaromatic capsule: unusual selectivity,isomerization, and volatility suppression

Cyclic monoterpenes (CMTs) are intractable natural products with high volatility and strong odors so that there has been no molecular receptor capable of selectively and tightly trapping CMTs in both solution and the solid state. We herein report that a polyaromatic capsule acts as a functional nanoflask for CMTs with the following five features: (i) the capsule can selectively bind menthone from mixtures with other saturated CMTs in water. In contrast, (ii) treatment of the capsule with mixtures of menthone and π-conjugated CMTs gives rise to ternary host–guest complexes with high pair-selectivity. Notably, (iii) the encapsulated menthone displays unusual isomerization from a typical chair conformer to otherwise unstable conformers upon heating. (iv) The selective binding of volatilized CMTs is demonstrated by the capsule even in the solid state at atmospheric pressure. Furthermore, (v) the volatilities of CMTs are significantly suppressed at elevated temperatures by the capsule upon encapsulation in solution as well as in the solid state.

A polyaromatic capsule demonstrated its unique host functions toward cyclic monoterpenes, i.e., selective binding in water, pair-selective encapsulation, unusual isomerization, selective binding in the solid state, and remarkable volatility suppression.     

Towards multistate multimode landscapes in singlet fission of pentacene: the dual role of charge-transfer states

Singlet fission duplicates triplet excitons for improving light harvesting efficiency. The presence of the interaction between electronic and nuclear degrees of freedom complicates the interpretation of correlated triplet pairs. We report a quantum chemistry study on the significance and subtleties of multistate and multimode pathways in forming triplet pair states of the pentacene dimer through a six-state vibronic-coupling Hamiltonian derived from many-electron adiabatic wavefunctions of an ab initio density matrix renormalization group. The resulting spin values of the singlet manifolds on each pentacene center are computed, and the varying spin nature can be distinguished clearly with respect to dimer stacking and vibronic progression. Our monomer spin assignments reveal the coexistence of both lower-lying weak and higher-lying strong charge transfer states which interact vibronically with the triplet pair state, providing important implications for its generation and separation occurring in vibronic regions. This work conveys the importance of the many-electron process requiring close low-lying singlet manifolds to determine the subtle fission details, and represents an important step for understanding vibronically resolved spin states and conversions underlying efficient singlet fission.

Singlet fission in pentacene necessitates the vibronic progression of weak and strong charge-transfer states with correlated triplet pairs.     

Multi-stimuli programmable FRET based RGB absorbing antennae towards ratiometric temperature,pH and multiple metal ion sensing

A red-green-blue (RGB) multichromophoric antenna 1 consisting of energy donors naphthalimides and perylenediimides and a central aza-BODIPY energy acceptor along with two subchromophoric red-blue (RB 6) and green-blue (GB 12) antennae was designed that showed efficient cascade Förster resonance energy transfer (FRET). RGB antenna 1 showed pronounced temperature-dependent emission behaviour where emission intensities in green and red channels could be tuned in opposite directions by temperature giving rise to unique ratiometric sensing with a temperature sensitivity of 0.4% °C. RGB antenna 1 showed reversible absorption modulation selectively in the blue region (RGB ↔ RG) upon acid/base addition giving rise to pH sensing behaviour. Furthermore, RGB antenna 1 was utilized to selectively sense metal ions such as Co²⁺ and Fe³⁺ through a FRET turn-off mechanism induced by a redox process at the aza-BODIPY site that resulted in the selective spectral modulation of the red band (i.e., RGB → GB). Model antenna RB 6 showed white light emission with chromaticity coordinates (0.32, 0.33) on acid addition. Antennae 1, 6 and 12 also exhibited solution state electrochromic switching characterized by distinct colour changes upon changing the potential. Finally, antennae 1, 6 and 12 served as reversible fluorescent inks in PMMA/antenna blends whereby the emission colours could be switched or tuned using different stimuli such as acid vapour, temperature and metal ions.

RGB antennae consisting of naphthalimides, perylenediimides and aza-BODIPY with efficient FRET show unique ratiometric temperature sensing, metal sensing (FRET-off) and pH sensing through various stimuli sensitive band tuning.     

Skeletal remodeling of chalcone-based pyridinium salts to access isoindoline polycycles and their bridged derivatives

Simultaneous deconstructive ring-opening and skeletal reconstruction of an inert, aromatic pyridinium ring is of great importance in synthetic communities. However, research in this area is still in its infancy. Here, a skeletal re-modeling strategy was developed to transform chalcone-based pyridinium salts into structurally intriguing polycyclic isoindolines through a dearomative ring-opening/ring-closing sequence. Two distinct driving forces for the deconstruction of the pyridinium core were involved in these transformations. One was the unprecedented harnessing of the instability of in situ generated cyclic β-aminoketones, and the other was the instability of the resultant N,N-ketals. The desired isoindoline polycycles could undergo the Wittig reaction with various phosphorus ylides to achieve structural diversity and complexity. Notably, by tuning the Wittig conditions by addition of one equivalent of base, an additional bridged ring was introduced. A plausible mechanism was proposed on the basis of control experiments and theoretical calculations.

A novel skeletal remodeling strategy to transform chalcone-based pyridinium salts into structurally intriguing polycyclic isoindolines was achieved through a dearomative ring-opening/ring-closing sequence.     

Borinostats: solid-phase synthesis of carborane-capped histone deacetylase inhibitors with a tailor-made selectivity profile

The elevated expression of histone deacetylases (HDACs) in various tumor types renders their inhibition an attractive strategy for epigenetic therapeutics. One key issue in the development of improved HDAC inhibitors (HDACis) is the selectivity for single HDAC isoforms over unspecific pan inhibition to minimize off-target toxicity. Utilizing the carborane moiety as a fine-tuning pharmacophore, we herein present a robust solid phase synthetic approach towards tailor-made HDACis meeting both ends of the selectivity spectrum, namely pan inhibition and highly selective HDAC6 inhibition.

This work describes a versatile solid phase synthesis of carborane-capped histone deacetylase inhibitors with a tunable selectivity profile and synergistic anticancer activity with bortezomib.     

Formally exact simulations of mesoscale exciton dynamics in molecular materials

Excited state carriers, such as excitons, can diffuse on the 100 nm to micron length scale in molecular materials but only delocalize over short length scales due to coupling between electronic and vibrational degrees-of-freedom. Here, we leverage the locality of excitons to adaptively solve the hierarchy of pure states equations (HOPS). We demonstrate that our adaptive HOPS (adHOPS) methodology provides a formally exact and size-invariant (i.e., ) scaling algorithm for simulating mesoscale quantum dynamics. Finally, we provide proof-of-principle calculations for exciton diffusion on linear chains containing up to 1000 molecules.

The adaptive hierarchy of pure states (adHOPS) algorithm leverages the locality of excitons in molecular materials to perform formally-exact simulations with size-invariant (i.e., ) scaling, enabling efficient simulations of mesoscale exciton dynamics.     

Achieving flexible large-scale reactivity tuning by controlling the phase,thickness and support of two-dimensional ZnO

Tuning surface reactivity of catalysts is an effective strategy to enhance catalytic activity towards a chemical reaction. Traditional reactivity tuning usually relies on a change of the catalyst composition, especially when large-scale tuning is desired. Here, based on density functional theory calculations, we provide a strategy for flexible large-scale tuning of surface reactivity, i.e. from a few tenths of electronvolts (eV) to multiple eV, merely through manipulating the phase, thickness, and support of two-dimensional (2D) ZnO films. 2D ZnO films have three typical phases, i.e. graphene, wurtzite, and body-centered-tetragonal structures, whose intrinsic stability strongly depends on the thickness and/or the chemical nature of the support. We show that the adsorption energy of hydrogen differs by up to 3 eV on these three phases. For the same phase, varying the film thickness and/or support can lead to a few tenths of eV to 2 eV tuning of surface reactivity. We further demonstrate that flexible large-scale tuning of surface reactivity has a profound impact on the reaction kinetics, including breaking the Brønsted–Evans–Polanyi relationship.

Flexible large-scale reactivity tuning is achieved by manipulating the phase, thickness and support of two-dimensional ZnO, and a broken scaling relationship between adsorption and barrier is found via phase and termination engineering.     

Controlling hydrogel properties by tuning non-covalent interactions in a charge complementary multicomponent system

Mixing small molecule gelators is a promising route to prepare useful and exciting materials that cannot be accessed from any of the individual components. Here, we describe pH-triggered hydrogelation by mixing of two non-gelling amphiphiles. The intermolecular interactions among the molecules can be tuned either by controlling the degree of ionization of the components or by a preparative pathway, which enables us to control material properties such as gel strength, gel stiffness, thermal stability, and an unusual shrinking/swelling behaviour.

The properties of a charge complementary multicomponent gel can be tuned either by pH change or by varying the preparative pathway.     

Direct air capture of CO2via crystal engineering

This article presents a perspective view of the topic of direct air capture (DAC) of carbon dioxide and its role in mitigating climate change, focusing on a promising approach to DAC involving crystal engineering of metal–organic and hydrogen-bonded frameworks. The structures of these crystalline materials can be easily elucidated using X-ray and neutron diffraction methods, thereby allowing for systematic structure–property relationships studies, and precise tuning of their DAC performance.

A perspective view of direct air capture (DAC) of CO₂ and its role in mitigating climate change is presented. The article focuses on a promising approach to DAC involving crystal engineering of metal–organic and hydrogen-bonded frameworks.     

Enhancement of Chiroptical Responses of trans‐Bis[(β‐iminomethyl)naphthoxy]platinum(II) Complexes with Distorted Square Planar Coordination Geometry

Invited for this month''s cover picture are the groups of Masahiro Ikeshita and Takashi Tsuno at Nihon University and Yoshitane Imai at Kindai University (Japan). The cover picture shows the comparison of circularly polarized luminescence (CPL) properties of square planar platinum(II) complexes with different coordination geometry. Computational studies have been carried out to investigate these structure‐dependencies, and revealed that the distortion of the coordination geometry results into an enhancement the chiroptical responses of these compounds. Read the full text of their Research Article at 10.1002/open.202100277.

“… How does the stereochemistry of transition metal complexes affect their photophysical properties…” Find out more about the story behind the front cover research at 10.1002/open.202100277.     

Controlled coherent dynamics of [VO(TPP)], a prototype molecular nuclear qudit with an electronic ancilla

We show that [VO(TPP)] (vanadyl tetraphenylporphyrinate) is a promising system to implement quantum computation algorithms based on encoding information in multi-level (qudit) units. Indeed, it embeds a nuclear spin 7/2 coupled to an electronic spin 1/2 by hyperfine interaction. This qubit–qudit unit can be exploited to implement quantum error correction and quantum simulation algorithms. Through a combined theoretical and broadband nuclear magnetic resonance study, we demonstrate that the elementary operations of such algorithms can be efficiently implemented on the nuclear spin qudit. Manipulation of the nuclear qudit can be achieved by resonant radio-frequency pulses, thanks to the remarkably long coherence times and the effective quadrupolar coupling induced by the strong hyperfine interaction. This approach may open new perspectives for developing new molecular qubit–qudit systems.

By a combined theoretical and broadband nuclear magnetic resonance study, we show that [VOTPP] is a coupled electronic qubit-nuclear qudit system suitable to implement qudit-based quantum error correction and quantum simulation algorithms.     

Arene–perfluoroarene interactions confer enhanced mechanical properties to synthetic nanotubes

Supramolecular nanotubes prepared through macrocycle assembly offer unique properties that stem from their long-range order, structural predictability, and tunable microenvironments. However, assemblies that rely on weak non-covalent interactions often have limited aspect ratios and poor mechanical integrity, which diminish their utility. Here pentagonal imine-linked macrocycles are prepared by condensing a pyridine-containing diamine and either terephthalaldehyde or 2,3,5,6-tetrafluoroterephthalaldehyde. Atomic force microscopy and synchrotron in solvo X-ray diffraction demonstrate that protonation of the pyridine groups drives assembly into high-aspect ratio nanotube assemblies. A 1 : 1 mixture of each macrocycle yielded nanotubes with enhanced crystallinity upon protonation. UV-Vis and fluorescence spectroscopy indicate that nanotubes containing both arene and perfluoroarene subunits display spectroscopic signatures of arene–perfluoroarene interactions. Touch-spun polymeric fibers containing assembled nanotubes prepared from the perhydro- or perfluorinated macrocycles exhibited Young''s moduli of 1.09 and 0.49 GPa, respectively. Fibers containing nanotube assemblies reinforced by arene–perfluoroarene interactions yielded a 93% increase in the Young''s modulus over the perhydro derivative, up to 2.1 GPa. These findings demonstrate that tuning the chemical composition of the monomeric macrocycles can have profound effects on the mechanical strength of the resulting assemblies. More broadly, these results will inspire future studies into tuning orthogonal non-covalent interactions between macrocycles to yield nanotubes with emergent functions and technological potential.

Arene–perfluoroarene interactions resulted in enhanced crystallinity between analogous perhydro- and perfluoro macrocycles in a supramolecular nanotube assembly.     

Controlling cyclization pathways in palladium(ii)-catalyzed intramolecular alkene hydro-functionalization via substrate directivity

We report a series of palladium(ii)-catalyzed, intramolecular alkene hydrofunctionalization reactions with carbon, nitrogen, and oxygen nucleophiles to form five- and six-membered carbo- and heterocycles. In these reactions, the presence of a proximal bidentate directing group controls the cyclization pathway, dictating the ring size that is generated, even in cases that are disfavored based on Baldwin''s rules and in cases where there is an inherent preference for an alternative pathway. DFT studies shed light on the origins of pathway selectivity in these processes.

We report a series of palladium(ii)-catalyzed, intramolecular alkene hydrofunctionalization reactions with carbon, nitrogen, and oxygen nucleophiles to form five- and six-membered carbo- and heterocycles.     

Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode

Bifurcating reactions yield two different products emerging from one single transition state and are therefore archetypal examples of reactions that cannot be described within the framework of the traditional Eyring''s transition state theory (TST). With the growing number and importance of these reactions in organic and biosynthetic chemistry, there is also an increasing demand for a theoretical tool that would allow for the accurate quantification of reaction outcome at low cost. Here, we introduce such an approach that fulfils these criteria, by evaluating bifurcation selectivity through the energy distribution within the reactive mode of the key transition state. The presented method yields an excellent agreement with experimentally reported product ratios and predicts the correct selectivity for 89% of nearly 50 various cases, covering pericyclic reactions, rearrangements, fragmentations and metal-catalyzed processes as well as a series of trifurcating reactions. With 71% of product ratios determined within the error of less than 20%, we also found that the methodology outperforms three other tested protocols introduced recently in the literature. Given its predictive power, the procedure makes reaction design feasible even in the presence of complex non-TST chemical steps.

Reactive Mode Composition Factor (RMCF) analysis is a powerful tool to forecast the product distribution of bifurcating reactions through analysis of the kinetic energy distribution within the first transition state traversed by the reacting system.     

Supramolecular chemistry in lipid bilayer membranes

Lipid bilayer membranes form compartments requisite for life. Interfacing supramolecular systems, including receptors, catalysts, signal transducers and ion transporters, enables the function of the membrane to be controlled in artificial and living cellular compartments. In this perspective, we take stock of the current state of the art of this rapidly expanding field, and discuss prospects for the future in both fundamental science and applications in biology and medicine.

This perspective provides an overview of the current state of the art in supramolecular chemistry in lipid bilayer membranes, including receptors, signal transducers, catalysts and transporters, and highlights prospects for the future.