Impact of the macrocyclic structure and dynamic solvent effect on the reactivity of a localised singlet diradicaloid with π-single bonding character

Localised singlet diradicals are key intermediates in bond homolysis processes. Generally, these highly reactive species undergo radical–radical coupling reaction immediately after their generation. Therefore, their short-lived character hampers experimental investigations of their nature. In this study, we implemented the new concept of “stretch effect” to access a kinetically stabilised singlet diradicaloid. To this end, a macrocyclic structure was computationally designed to enable the experimental examination of a singlet diradicaloid with π-single bonding character. The kinetically stabilised diradicaloid exhibited a low carbon–carbon coupling reaction rate of 6.4 × 10³ s⁻¹ (155.9 μs), approximately 11 and 1000 times slower than those of the first generation of macrocyclic system (7.0 × 10⁴ s⁻¹, 14.2 μs) and the parent system lacking the macrocycle (5 × 10⁶ s⁻¹, 200 ns) at 293 K in benzene, respectively. In addition, a significant dynamic solvent effect was observed for the first time in intramolecular radical–radical coupling reactions in viscous solvents such as glycerin triacetate. This theoretical and experimental study demonstrates that the stretch effect and solvent viscosity play important roles in retarding the σ-bond formation process, thus enabling a thorough examination of the nature of the singlet diradicaloid and paving the way toward a deeper understanding of reactive intermediates.

An extremely long-lived localised singlet diradical with π-single bonding character is found in a macrocyclic structure that retards the radical–radical coupling reaction by the “stretch and solvent-dynamic effects”.     

Efficient Photoelectrochemical Energy Conversion using Spinach Photosystem II (PSII) in Lipid Multilayer Films

The need for clean, renewable energy has fostered research into photovoltaic alternatives to silicon solar cells. Pigment–protein complexes in green plants convert light energy into chemical potential using redox processes that produce molecular oxygen. Here, we report the first use of spinach protein photosystem II (PSII) core complex in lipid films in photoelectrochemical devices. Photocurrents were generated from PSII in a ∼2 μm biomimetic dimyristoylphosphatidylcholine (DMPC) film on a pyrolytic graphite (PG) anode with PSII embedded in multiple lipid bilayers. The photocurrent was ∼20 μA cm⁻² under light intensity 40 mW cm⁻². The PSII–DMPC anode was used in a photobiofuel cell with a platinum black mesh cathode in perchloric acid solution to give an output voltage of 0.6 V and a maximum output power of 14 μW cm⁻². Part of this large output is related to a five-unit anode–cathode pH gradient. With catholytes at higher pH or no perchlorate, or using an MnO₂ oxygen-reduction cathode, the power output was smaller. The results described raise the possibility of using PSII–DMPC films in small portable power conversion devices.     

A reduced-dimensional polar hybrid perovskite for self-powered broad-spectrum photodetection

Polar hybrid perovskites have been explored for self-powered photodetection benefitting from prominent transport of photo-induced carriers and the bulk photovoltaic effect (BPVE). However, these self-powered photodetection ranges are relatively narrow depending on their intrinsic wide bandgaps (>2.08 eV), and the realization of broad-spectrum self-powered photodetection is still a difficult task. Herein, we successfully obtained a polar multilayered perovskite, (I-BA)₂(MA)₂Pb₃I₁₀ (IMP, MA⁺ = methylammonium and I-BA⁺ = 4-iodobutylammonium), via rational dimension reduction of CH₃NH₃PbI₃. It features the narrowest bandgap of 1.71 eV in a BPV material. As a consequence, the integration of narrow bandgap and BPVE causes the self-powered photodetection to extend to 724 nm for IMP, and a repeatable photovoltaic current reaching 1.0 μA cm⁻² is acquired with a high “on/off” ratio of ∼10³ and photodetectivity (∼10⁹ Jones) at zero bias. This innovative research provides a foothold for adjusting the physical properties of hybrid perovskites and will expand their potential for self-powered broad-spectrum detection.

A polar hybrid perovskite with a wide-spectrum absorption extending to 724 nm was obtained . Benefitting from the narrow bandgap and bulk photovoltaic effects, self-powered broad-spectrum photodetection was achieved in hybrid perovskites.     

Challenges and prospects of ambient hybrid solar cell applications

The impending implementation of billions of Internet of Things and wireless sensor network devices has the potential to be the next digital revolution, if energy consumption and sustainability constraints can be overcome. Ambient photovoltaics provide vast universal energy that can be used to realise near-perpetual intelligent IoT devices which can directly transform diffused light energy into computational inferences based on artificial neural networks and machine learning. At the same time, a new architecture and energy model needs to be developed for IoT devices to optimize their ability to sense, interact, and anticipate. We address the state-of-the-art materials for indoor photovoltaics, with a particular focus on dye-sensitized solar cells, and their effect on the architecture of next generation IoT devices and sensor networks.

The impending implementation of billions of Internet of Things and wireless sensor network devices has the potential to be the next digital revolution, if energy consumption and sustainability constraints can be overcome.     

Pinkment: a synthetic platform for the development of fluorescent probes for diagnostic and theranostic applications

Reaction-based fluorescent-probes have proven successful for the visualisation of biological species in various cellular processes. Unfortunately, in order to tailor the design of a fluorescent probe to a specific application (i.e. organelle targeting, material and theranostic applications) often requires extensive synthetic efforts and the synthetic screening of a range of fluorophores to match the required synthetic needs. In this work, we have identified Pinkment-OH as a unique “plug-and-play” synthetic platform that can be used to develop a range of ONOO⁻ responsive fluorescent probes for a variety of applications. These include theranostic-based applications and potential material-based/bioconjugation applications. The as prepared probes displayed an excellent sensitivity and selectivity for ONOO⁻ over other ROS. In vitro studies using HeLa cells and RAW 264.7 macrophages demonstrated their ability to detect exogenously and endogenously produced ONOO⁻. Evaluation in an LPS-induced inflammation mouse model illustrated the ability to monitor ONOO⁻ production in acute inflammation. Lastly, theranostic-based probes enabled the simultaneous evaluation of indomethacin-based therapeutic effects combined with the visualisation of an inflammation biomarker in RAW 264.7 cells.

Pinkment, a resorufin based ONOO⁻ selective and sensitive ‘plug and play’ fluorescence-based platform for in vitro and in vivo use, enables facile functionalisation for various imaging and theranostic applications.     

Coordination polymer glass from a protic ionic liquid: proton conductivity and mechanical properties as an electrolyte

High proton conducting electrolytes with mechanical moldability are a key material for energy devices. We propose an approach for creating a coordination polymer (CP) glass from a protic ionic liquid for a solid-state anhydrous proton conductor. A protic ionic liquid (dema)(H₂PO₄), with components which also act as bridging ligands, was applied to construct a CP glass (dema)_0.35[Zn(H₂PO₄)_2.35(H₃PO₄)_0.65]. The structural analysis revealed that large Zn–H₂PO₄⁻/H₃PO₄ coordination networks formed in the CP glass. The network formation results in enhancement of the properties of proton conductivity and viscoelasticity. High anhydrous proton conductivity (σ = 13.3 mS cm⁻¹ at 120 °C) and a high transport number of the proton (0.94) were achieved by the coordination networks. A fuel cell with this CP glass membrane exhibits a high open-circuit voltage and power density (0.15 W cm⁻²) under dry conditions at 120 °C due to the conducting properties and mechanical properties of the CP glass.

A proton-conducting coordination polymer glass derived from a protic ionic liquid works as a moldable solid electrolyte and the anhydrous fuel cell showed I–V performance of 0.15 W cm⁻² at 120 °C.     

Combining alkali metals and zinc to harness heterometallic cooperativity in cyclic ester ring-opening polymerisation

Heterometallic cooperativity is an emerging strategy to elevate polymerisation catalyst performance. Here, we report the first heterotrimetallic Na/Zn₂ and K/Zn₂ complexes supported by a ProPhenol ligand, which deliver “best of both” in cyclic ester ring-opening polymerisation, combining the outstanding activity (Na/K) and good control (Zn₂) of homometallic analogues. Detailed NMR studies and density-functional theory calculations suggest that the Na/Zn₂ and K/Zn₂ complexes retain their heterometallic structures in the solution-state. To the best of our knowledge, the K/Zn₂ analogue is the most active heterometallic catalyst reported for rac-lactide polymerisation (k_obs = 1.7 × 10⁻² s⁻¹), giving activities five times faster than the Na/Zn₂ complex. These versatile catalysts also display outstanding performance in ε-caprolatone and δ-valerolactone ring-opening polymerisation. These studies provide underpinning methodologies for future heterometallic polymerisation catalyst design, both in cyclic ester polymerisation and other ring-opening (co)polymerisation reactions.

Cooperative heterotrimetallic Na/Zn₂ and K/Zn₂ complexes combine the excellent activities and control of the homometallic analogues, giving “best of both” in cyclic ester ring-opening polymerisation.     

A protecting group strategy to access stable lacunary polyoxomolybdates for introducing multinuclear metal clusters

Although metal-containing polyoxomolybdates (molybdenum oxide clusters) exhibit outstanding catalytic properties, their precise synthetic method has not yet been developed. This is mainly because the very low stability of the multivacant lacunary polyoxomolybdates limited their use as synthetic precursors. Here, we present a “protecting group strategy” in polyoxometalate synthesis and successfully develop an efficient method for synthesising multinuclear metal-containing polyoxomolybdates using pyridine as a protecting group for unstable trivacant lacunary Keggin-type polyoxomolybdate [PMo₉O₃₄]⁹⁻. Specifically, tetranuclear cubane- and planar-type manganese clusters were selectively synthesised in the polyoxomolybdates using the present method. The importance of this work is that, in addition to being the first practical way of utilizing multivacant lacunary polyoxomolybdates as precursors, this new “protecting group strategy” will make it possible to produce polyoxometalates with unexplored structures and properties.

A “protecting group strategy” for unstable lacunary polyoxomolybdates enabled successful synthesis of two types of tetranuclear manganese clusters.     

Extremely low-frequency phonon material and its temperature- and photo-induced switching effects

Atomic vibrations due to stretching or bending modes cause optical phonon modes in the solid phase. These optical phonon modes typically lie in the frequency range of 10² to 10⁴ cm⁻¹. How much can the frequency of optical phonon modes be lowered? Herein we show an extremely low-frequency optical phonon mode of 19 cm⁻¹ (0.58 THz) in a Rb-intercalated two-dimensional cyanide-bridged Co–W bimetal assembly. This ultralow frequency is attributed to a millefeuille-like structure where Rb ions are very softly sandwiched between the two-dimensional metal–organic framework, and the Rb ions slowly vibrate between the layers. Furthermore, we demonstrate temperature-induced and photo-induced switching of this low-frequency phonon mode. Such an external-stimulation-controllable sub-terahertz (sub-THz) phonon crystal, which has not been reported before, should be useful in devices and absorbers for high-speed wireless communications such as beyond 5G or THz communication systems.

Extremely low-frequency optical phonon mode in Rb-intercalated two-dimensional cyanide-bridged Co–W bimetal assembly and its temperature- and photo-induced switching effect.     

Understanding the geometric diversity of inorganic and hybrid frameworks through structural coarse-graining

Much of our understanding of complex structures is based on simplification: for example, metal–organic frameworks are often discussed in the context of “nodes” and “linkers”, allowing for a qualitative comparison with simpler inorganic structures. Here we show how such an understanding can be obtained in a systematic and quantitative framework, combining atom-density based similarity (kernel) functions and unsupervised machine learning with the long-standing idea of “coarse-graining” atomic structure. We demonstrate how the latter enables a comparison of vastly different chemical systems, and we use it to create a unified, two-dimensional structure map of experimentally known tetrahedral AB₂ networks – including clathrate hydrates, zeolitic imidazolate frameworks (ZIFs), and diverse inorganic phases. The structural relationships that emerge can then be linked to microscopic properties of interest, which we exemplify for structural heterogeneity and tetrahedral density.

A coarse-graining approach enables structural comparisons across vastly different chemical spaces, from inorganic polymorphs to hybrid framework materials.     

Achieving high circularly polarized luminescence with push–pull helicenic systems: from rationalized design to top-emission CP-OLED applications

While the development of chiral molecules displaying circularly polarized luminescence (CPL) has received considerable attention, the corresponding CPL intensity, g_lum, hardly exceeds 10⁻² at the molecular level owing to the difficulty in optimizing the key parameters governing such a luminescence process. To address this challenge, we report here the synthesis and chiroptical properties of a new family of π-helical push–pull systems based on carbo[6]helicene, where the latter acts as either a chiral electron acceptor or a donor unit. This comprehensive experimental and theoretical investigation shows that the magnitude and relative orientation of the electric (μ_e) and magnetic (μ_m) dipole transition moments can be tuned efficiently with regard to the molecular chiroptical properties, which results in high g_lum values, i.e. up to 3–4 × 10⁻². Our investigations revealed that the optimized mutual orientation of the electric and magnetic dipoles in the excited state is a crucial parameter to achieve intense helicene-mediated exciton coupling, which is a major contributor to the obtained strong CPL. Finally, top-emission CP-OLEDs were fabricated through vapor deposition, which afforded a promising g_El of around 8 × 10⁻³. These results bring about further molecular design guidelines to reach high CPL intensity and offer new insights into the development of innovative CP-OLED architectures.

A CPL intensity of up to 3 × 10⁻² is achieved in π-extended 6-helicene derivatives, owing to an intense helicene-mediated exciton coupling. Corresponding top-emission CP-OLEDs afforded a promising g_El of around 8 × 10⁻³.

The design of chiral emitters displaying intense circularly polarized luminescence (CPL) has attracted significant interest, thanks to the potential of CP light in a diverse range of applications going from chiroptoelectronics (organic light-emitting diodes (OLEDs), optical information processing, etc.) to bio-imaging and chiral sensing.¹ Recently, designing OLEDs with CP electroluminescence (CP-OLEDs) has emerged as an interesting approach to improve high-resolution display performance. Namely, using unpolarised OLEDs, up to 50% of the emitted light can be lost due to the use of antiglare polarized filters.² In CP-OLEDs, the electro-generated light can pass these filters with less attenuation owing to its circular polarization and thus lead to an increase of the image brightness with lower power consumption.³ To develop CP-OLED devices, the main approach relies on the doping of the device''s emitting layer by a CPL emitter, which should ensure simultaneously high exciton conversion and a high degree of circular polarization. The harvesting of both singlet and triplet excitons has been successfully addressed using either chiral phosphorescent materials or thermally activated delayed fluorescence (CP-TADF) emitters with device efficiencies of up to 32%.⁴ However, the intensity of circularly polarized electroluminescence (CPEL), evaluated by the corresponding dissymmetry factor g_El, remains inefficient and typically falls within the range of 10⁻³ with limited examples reaching g_El > 10⁻² based on polymeric materials and lanthanide complexes.⁵ For CP-OLEDs using a molecular chiral emissive dopant, g_El, defined as the ratio between the intensity difference of left- and right-CPEL, and the total generated electroluminescence, 2(El_L − El_R)/(El_L + El_R), can be generally related to the luminescence dissymmetry factor g_lum measured in diluted solution.² Accordingly, it is of crucial importance to design luminescent molecules with high g_lum values,^3,28a–d,29 in order to reach strong CP electro-luminescence when going to practical devices. However, structural and electronic factors that govern the CPL of chiral compounds are still poorly understood even if a few studies have recently tried to rationalize and establish molecular guidelines to obtain high g_lum values.⁶Our team has contributed to the research in this area by developing extended π-helical molecular architectures resulting from the association of carbo[6]helicene and achiral dyes,⁷ which afforded enhanced chiroptical properties, with notably a g_lum up to 10⁻², owing to an uncommon chiral exciton coupling process mediated by the chiral helicenic unit.⁸ In addition, we also described an unusual solvent effect on the intensity of CPL of π-helical push–pull helicene–naphthalimide derivatives,^7b which showed a decrease of g_lum from 10⁻² to 10⁻³ upon increasing the polarity of solvent.^7b This solvatochromism effect was shown to be related to a symmetry breaking of the chiral excited state before emission,⁹ which modifies the relative intensity of the magnetic (μ_m) and electric (μ_e) dipole transition moments, and the angle, θ, between them (Fig. 1), ultimately impacting g_lum. The latter is well approximated as 4|m|cos θ/(|μ|) for an electric dipole-allowed transition.¹⁰Open in a separate windowFig. 1Chemical structures of “push–pull” 2,15-diethynylhexahelicene-based emitters with their polarized luminescence characteristics including their calculated electric and magnetic transition dipole moments and the angle between them corresponding to the S₁ → S₀ transition.While these results highlight interesting aspects regarding the key parameters influencing the CPL of organic emitters, this type of “helical push–pull design” remains limited to only one example, which render the systematic rationalization of these findings difficult. Accordingly, we decided to develop a complete family of new chiral push–pull compounds to explore the structural and electronic impact of the grafted substituents on the helical π-conjugated system. In addition, we went a step further and incorporated the designed chiral emitter into proof-of-concept CP-OLEDs using a top-emission architecture,¹¹ which remains scarcely explored for CP-light generation despite its considerable potential for micro-display applications. To the best of our knowledge, only one example of such type of electroluminescent device has been reported, using a CP-TADF emitter, affording a modest g_El of 10⁻³.^11aHerein, we report the synthesis and chiroptical properties of a new family of π-helical push–pull systems based on chiral carbo[6]helicene, functionalized by either electron donor or acceptor units. Interestingly, the chiral π-conjugated system of the helicene may act as either an electron acceptor or a donor, depending on the nature of the attached substituents, thereby impacting the chiroptical properties, notably the resulting CPL. By optimizing the chiral exciton coupling process through the modulation of the magnitude and relative orientation of the electric (μ) and magnetic (m) dipoles, the chiroptical properties of classical carbo[6]helicene-based emitters can be dramatically enhanced and reach high g_lum values at the molecular level, i.e. up to 3–4 × 10⁻². Experimental and theoretical investigations revealed that the mutual orientation of the electric and magnetic dipoles in the excited-state is a crucial parameter and is optimal when the substituents attached to the helicene core possess a rather weak electron withdrawing or donating ability. Finally, proof of concept top-emission CP-OLEDs were fabricated through vapor deposition of π-helical push–pull derivatives and afforded a g_El of around 8 × 10⁻³, which represents a significant improvement for the polarization of electroluminescence emitted using this device architecture.     

Proton-conductive coordination polymer glass for solid-state anhydrous proton batteries

Designing solid-state electrolytes for proton batteries at moderate temperatures is challenging as most solid-state proton conductors suffer from poor moldability and thermal stability. Crystal–glass transformation of coordination polymers (CPs) and metal–organic frameworks (MOFs) via melt-quenching offers diverse accessibility to unique properties as well as processing abilities. Here, we synthesized a glassy-state CP, [Zn₃(H₂PO₄)₆(H₂O)₃](1,2,3-benzotriazole), that exhibited a low melting temperature (114 °C) and a high anhydrous single-ion proton conductivity (8.0 × 10⁻³ S cm⁻¹ at 120 °C). Converting crystalline CPs to their glassy-state counterparts via melt-quenching not only initiated an isotropic disordered domain that enhanced H⁺ dynamics, but also generated an immersive interface that was beneficial for solid electrolyte applications. Finally, we demonstrated the first example of a rechargeable all-solid-state H⁺ battery utilizing the new glassy-state CP, which exhibited a wide operating-temperature range of 25 to 110 °C.

Melt-quenched coordination polymer glass shows exclusive H⁺ conductivity (8.0 × 10⁻³ S cm⁻¹ at 120 °C, anhydrous) and optimal mechanical properties (42.8 Pa s at 120 °C), enables the operation of an all-solid-state proton battery from RT to 110 °C.     

Solvate sponge crystals of (DMF)3NaClO4: reversible pressure/temperature controlled juicing in a melt/press-castable sodium-ion conductor

A new type of crystalline solid, termed “solvate sponge crystal”, is presented, and the chemical basis of its properties are explained for a melt- and press-castable solid sodium ion conductor. X-ray crystallography and atomistic simulations reveal details of atomic interactions and clustering in (DMF)₃NaClO₄ and (DMF)₂NaClO₄ (DMF = N-N′-dimethylformamide). External pressure or heating results in reversible expulsion of liquid DMF from (DMF)₃NaClO₄ to generate (DMF)₂NaClO₄. The process reverses upon the release of pressure or cooling. Simulations reveal the mechanism of crystal “juicing,” as well as melting. In particular, cation–solvent clusters form a chain of octahedrally coordinated Na⁺–DMF networks, which have perchlorate ions present in a separate sublattice space in 3 : 1 stoichiometry. Upon heating and/or pressing, the Na⁺⋯DMF chains break and the replacement of a DMF molecule with a ClO₄⁻ anion per Na⁺ ion leads to the conversion of the 3 : 1 stoichiometry to a 2 : 1 stoichiometry. The simulations reveal the anisotropic nature of pressure induced stoichiometric conversion. The results provide molecular level understanding of a solvate sponge crystal with novel and desirable physical castability properties for device fabrication.

Stimuli-responsive “solvate-sponge”-(DMF)₃NaClO₄ exhibits linear chains of DMF–Na⁺ ions with ClO₄⁻ anions in the interstitial space. At increased pressure or temperature, DMF is expelled (reversibly), resulting in a new stoichiometry-(DMF)₂NaClO₄.     

A generator of peroxynitrite activatable with red light

The generation of reactive oxygen species (ROS) and reactive nitrogen species (RNS) as “unconventional” therapeutics with precise spatiotemporal control by using light stimuli may open entirely new horizons for innovative therapeutic modalities. Among ROS and RNS, peroxynitrite (ONOO⁻) plays a dominant role in chemistry and biology in view of its potent oxidizing power and cytotoxic action. We have designed and synthesized a molecular hybrid based on benzophenothiazine as a red light-harvesting antenna joined to an N-nitroso appendage through a flexible spacer. Single photon red light excitation of this molecular construct triggers the release of nitric oxide (˙NO) and simultaneously produces superoxide anions (O₂˙⁻). The diffusion-controlled reaction between these two radical species generates ONOO⁻, as confirmed by the use of fluorescein-boronate as a highly selective chemical probe. Besides, the red fluorescence of the hybrid allows its tracking in different types of cancer cells where it is well-tolerated in the dark but induces remarkable cell mortality under irradiation with red light in a very low concentration range, with very low light doses (ca. 1 J cm⁻²). This ONOO⁻ generator activatable by highly biocompatible and tissue penetrating single photon red light can open up intriguing prospects in biomedical research, where precise and spatiotemporally controlled concentrations of ONOO⁻ are required.

Excitation of a molecular hybrid with highly biocompatible red light generates cytotoxic peroxynitrite, produces red fluorescence useful for cell tracking and induces remarkable cancer cell death at very low concentrations and very low light doses.     

Fast Li-Ion Conduction in Spinel-Structured Solids

Spinel-structured solids were studied to understand if fast Li⁺ ion conduction can be achieved with Li occupying multiple crystallographic sites of the structure to form a “Li-stuffed” spinel, and if the concept is applicable to prepare a high mixed electronic-ionic conductive, electrochemically active solid solution of the Li⁺ stuffed spinel with spinel-structured Li-ion battery electrodes. This could enable a single-phase fully solid electrode eliminating multi-phase interface incompatibility and impedance commonly observed in multi-phase solid electrolyte–cathode composites. Materials of composition Li_1.25M(III)_0.25TiO₄, M(III) = Cr or Al were prepared through solid-state methods. The room-temperature bulk Li⁺-ion conductivity is 1.63 × 10⁻⁴ S cm⁻¹ for the composition Li_1.25Cr_0.25Ti_1.5O₄. Addition of Li₃BO₃ (LBO) increases ionic and electronic conductivity reaching a bulk Li⁺ ion conductivity averaging 6.8 × 10⁻⁴ S cm⁻¹, a total Li-ion conductivity averaging 4.2 × 10⁻⁴ S cm⁻¹, and electronic conductivity averaging 3.8 × 10⁻⁴ S cm⁻¹ for the composition Li_1.25Cr_0.25Ti_1.5O₄ with 1 wt. % LBO. An electrochemically active solid solution of Li_1.25Cr_0.25Mn_1.5O₄ and LiNi_0.5Mn_1.5O₄ was prepared. This work proves that Li-stuffed spinels can achieve fast Li-ion conduction and that the concept is potentially useful to enable a single-phase fully solid electrode without interphase impedance.     

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

An extremely bulky, symmetrical three-coordinate magnesium(i) complex, [{(^TCHPNacnac)Mg}₂] (^TCHPNacnac = [{(TCHP)NCMe}₂CH]⁻, TCHP = 2,4,6-tricyclohexylphenyl) has been prepared and shown to have an extremely long Mg–Mg bond (3.021(1) Å) for such a complex. It was shown not to react with either DMAP (4-dimethylaminopyridine) or CO. Three unsymmetrical 1 : 1 DMAP adducts of less bulky Mg–Mg bonded species have been prepared, viz. [(^ArNacnac)Mg–Mg(DMAP)(^ArNacnac)] (^ArNacnac = [(ArNCMe)₂CH]⁻ Ar = 2,6-xylyl (Xyl), mesityl (Mes) or 2,6-diethylphenyl (Dep)), and their reactivity toward CO explored. Like the previously reported bulkier complex, [(^DipNacnac)Mg–Mg(DMAP)(^DipNacnac)] (Dip = 2,6-diisopropylphenyl), [(^DepNacnac)Mg–Mg(DMAP)(^DepNacnac)] reductively trimerises CO to give a rare example of a deltate complex, [{(^DepNacnac)Mg(μ-C₃O₃)Mg(DMAP)(^DepNacnac)}₂]. In contrast, the two smaller adduct complexes react with only two CO molecules, ultimately giving unusual ethenediolate complexes [{(^ArNacnac)Mg{μ-OC(H) C(DMAP^−H)O}Mg(^ArNacnac)}₂] (Ar = Xyl or Mes). DFT calculations show the latter reactions to proceed via reductive dimerizations of CO, and subsequent intramolecular C–H activation of Mg-ligated DMAP by “zig–zag” [C₂O₂]²⁻ fragments of reaction intermediates. Calculations also suggest that magnesium deltate complexes are kinetic products in these reactions, while the magnesium ethenediolates are thermodynamic products. This study shows that subtle changes to the bulk of the reacting 1 : 1 DMAP–magnesium(i) adduct complexes can lead to fine steric control over the products arising from their CO reductive oligomerisations. Furthermore, it is found that the more activated nature of the adduct complexes, relative to their symmetrical, three-coordinate counterparts, [{(^ArNacnac)Mg}₂], likely derives more from the polarisation of the Mg–Mg bonds of the former, than the elongated nature of those bonds.

Subtle changes to the bulk of 1 : 1 adducts of DMAP with magnesium(i) complexes leads to steric control over the products arising from their reductive oligomerisations of carbon monoxide.      

Fluorescent probe for the imaging of superoxide and peroxynitrite during drug-induced liver injury

Drug-induced liver injury (DILI) is an important cause of potentially fatal liver disease. Herein, we report the development of a molecular probe (LW-OTf) for the detection and imaging of two biomarkers involved in DILI. Initially, primary reactive oxygen species (ROS) superoxide (O₂˙⁻) selectively activates a near-infrared fluorescence (NIRF) output by generating fluorophore LW-OH. The C C linker of this hemicyanine fluorophore is subsequently oxidized by reactive nitrogen species (RNS) peroxynitrite (ONOO⁻), resulting in cleavage to release xanthene derivative LW-XTD, detected using two-photon excitation fluorescence (TPEF). An alternative fluorescence pathway can occur through cleavage of LW-OTf by ONOO⁻ to non-fluorescent LW-XTD-OTf, which can react further with the second analyte O₂˙⁻ to produce the same LW-XTD fluorescent species. By combining NIRF and TPEF, LW-OTf is capable of differential and simultaneous detection of ROS and RNS in DILI using two optically orthogonal channels. Probe LW-OTf could be used to detect O₂˙⁻ or O₂˙⁻ and ONOO⁻ in lysosomes stimulated by 2-methoxyestradiol (2-ME) or 2-ME and SIN-1 respectively. In addition, we were able to monitor the chemoprotective effects of tert-butylhydroxyanisole (BHA) against acetaminophen (APAP) toxicity in living HL-7702 cells. More importantly, TPEF and NIRF imaging confirmed an increase in levels of both O₂˙⁻ and ONOO⁻ in mouse livers during APAP-induced DILI (confirmed by hematoxylin and eosin (H&E) staining).

Drug-induced liver injury (DILI) is an important cause of potentially fatal liver disease.     

An earth-abundant bimetallic catalyst coated metallic nanowire grown electrode with platinum-like pH-universal hydrogen evolution activity at high current density

A self-supported and flexible current collector solely made of earth-abundant elements, NiCo layered double hydroxide (LDH) wrapped around Cu nanowires (Cu-Ws) grown on top of commercially available Cu mesh (Cu-m), outperforms the benchmark 40 wt% Pt/C in catalyzing the electrochemical hydrogen evolution reaction (HER). The Cu-m/Cu-W/NiCo-LDH cathode operates both in acidic and alkaline media exhibiting high turnover frequencies (TOF) at 30 mV (0.3 H₂ s⁻¹ in 1 M KOH and 0.32 H₂ s⁻¹ in 0.5 M H₂SO₄, respectively) and minimal overpotentials of 15 ± 6 mV in 1 M KOH and 27 ± 2 mV in 0.5 M H₂SO₄ at −10 mA cm⁻². Cu-m/Cu-W/NiCo-LDH outperforms the activity of 40 wt% Pt/C that needs overpotentials of 22 and 18 mV in 1 M KOH and 0.5 M H₂SO₄, respectively. With a tremendous advantage over Pt/C in triggering proton reduction with fast kinetics, similar mass activity and pH-universality, the current collector demonstrates outstanding operational durability even at above −1 A cm⁻². The high density of electronic states near the Fermi energy level of Cu-Ws is found to be a pivotal factor for efficient electron transfer to the NiCo-LDH catalyst. This class of self-supported electrodes is expected to trigger rapid progress in developing high performance energy conversion and storage devices.

A flexible self-supported electrode made of earth-abundant elements, NiCo layered double hydroxide wrapped around Cu nanowires grown on Cu mesh, outperforms the benchmark 40 wt% Pt/C in catalyzing electrochemical hydrogen evolution reaction.     

Delocalization tunable by ligand substitution in [L2Al]n− complexes highlights a mechanism for strong electronic coupling

Ligand-based mixed valent (MV) complexes of Al(iii) incorporating electron donating (ED) and electron withdrawing (EW) substituents on bis(imino)pyridine ligands (I₂P) have been prepared. The MV states containing EW groups are both assigned as Class II/III, and those with ED functional groups are Class III and Class II/III in the (I₂P⁻)(I₂P²⁻)Al and [(I₂P²⁻)(I₂P³⁻)Al]²⁻ charge states, respectively. No abrupt changes in delocalization are observed with ED and EW groups and from this we infer that ligand and metal valence p-orbitals are well-matched in energy and the absence of LMCT and MLCT bands supports the delocalized electronic structures. The MV ligand charge states (I₂P⁻)(I₂P²⁻)Al and [(I₂P²⁻)(I₂P³⁻)Al]²⁻ show intervalence charge transfer (IVCT) transitions in the regions 6850–7740 and 7410–9780 cm⁻¹, respectively. Alkali metal cations in solution had no effect on the IVCT bands of [(I₂P²⁻)(I₂P³⁻)Al]²⁻ complexes containing –PhNMe₂ or –PhF₅ substituents. Minor localization of charge in [(I₂P²⁻)(I₂P³⁻)Al]²⁻ was observed when –PhOMe substituents are included.

Organo-aluminum mixed-valent complexes combine properties of both organic and transition element mixed-valent compounds. This supports delocalized electronic structures that are structurally and electronically tunable.