An Aluminum Telluride with a Terminal Al=Te Bond and its Conversion to an Aluminum Tellurocarbonate by CO2 Reduction

Facile access to dimeric heavier aluminum chalcogenides [(NHC)Al(Tipp)-μ-Ch]₂ (NHC=IiPr (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, IMe₄ (1,3,4,5-tetramethylimidazol-2-ylidene); Tipp=2,4,6-iPr₃C₆H₂; Ch=Se, Te) by treatment of NHC-stabilized aluminum dihydrides with elemental Se and Te is reported. The higher affinity of IMe₄ in comparison with IiPr toward the Al center in [(NHC)Al(Tipp)-μ-Ch]₂ can be used for ligand exchange. Additionally, the presence of excess IMe₄ allows for cleavage of the dimers to form a rare example of a neutral multiply bonded heavier aluminum chalcogenide in the form of a tetracoordinate aluminum complex, (IMe₄)₂(Tipp)Al=Te. This species reacts with three equivalents of CO₂ across two Al−C^NHC and the Al=Te bond affording a pentacoordinate aluminum complex containing a dianionic tellurocarbonate ligand [CO₂Te]²⁻, which is the first example of tellurium analogue of a carbonate [CO₃]²⁻.     

Stereospecific Oxycyanation of Alkenes with Sulfonyl Cyanide

Oxycyanation of alkenes would allow the direct construction of useful β-hydroxy nitrile scaffolds. However, only limited examples of such reactions have been reported, and some problems including limited substrate scope and the lack of diastereocontrol in the case of the oxycyanation of internal alkenes have arisen. We herein report on the intermolecular oxycyanation of alkenes using p-toluenesulfonyl cyanide (TsCN) in the presence of tris(pentafluorophenyl)borane (B(C₆F₅)₃) as a catalyst, affording products that contain a sulfinyloxy group and a cyano group at the vicinal position. The reaction features a stereospecific syn-addition. The reaction also shows a broad substrate scope with good functional group tolerance. Mechanistic investigations by experimental studies and density functional theory (DFT) calculations revealed that the reaction proceeds via an unprecedented stereospecific mechanism through the electrophilic cyanation of alkenes, in which B(C₆F₅)₃ efficiently activates TsCN through the coordination of the cyano group to the boron center.     

An Arbitrarily Regulated Monomer Sequence in Multi-Block Copolymer Synthesis by Frustrated Lewis Pairs

Rapid access to sequence-controlled multi-block copolymers (multi-BCPs) remains as a challenging task in the polymer synthesis. Here we employ a Lewis pair (LP) composed of organophosphorus superbase and bulky organoaluminum to effectively copolymerize the mixture of methacrylate, cyclic acrylate, and two acrylates, into well-defined di-, tri-, tetra- and even a hepta-BCP in one-pot one-step manner. The combined livingness, dual-initiation and CSC feature of Lewis pair polymerization enable us to achieve not only a trihexaconta-BCP with the highest record in 8 steps by using four-component monomer mixture as building blocks, but also the arbitrarily-regulated monomer sequence in multi-BCP, simply by changing the composition and adding order of the monomer mixtures, thus demonstrating the powerful capability of our strategy in improving the efficiency and enriching the composition of multi-BCP synthesis.     

Oxidation-Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2O2

The full reaction photosynthesis of H₂O₂ that can combine water-oxidation and oxygen-reduction without sacrificial agents is highly demanded to maximize the light-utilization and overcome the complex reaction-process of anthraquinone-oxidation. Here, a kind of oxidation-reduction molecular junction covalent-organic-framework (TTF-BT-COF) has been synthesized through the covalent-coupling of tetrathiafulvalene (photo-oxidation site) and benzothiazole (photo-reduction site), which presents visible-light-adsorption region, effective electron-hole separation-efficiency and photo-redox sites that enables full reaction generation of H₂O₂. Specifically, a record-high yield (TTF-BT-COF, ≈276 000 μM h⁻¹ g⁻¹) for H₂O₂ photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation-reduction molecular junction COFs for full reaction photosynthesis of H₂O₂, which might extend the scope of COFs in H₂O₂ production.     

Water-Stable Metal Azolate Frameworks Showing Interesting Flexibilities for Highly Effective Bioethanol Dehydration

The ethanol/water separation challenge highlights the adsorption capacity/selectivity trade-off problem. We show that the target guest can serve as a gating component of the host to block the undesired guest, giving molecular sieving effect for the adsorbent possessing large pores. Two hydrophilic/water-stable metal azolate frameworks were designed to compare the effects of gating and pore-opening flexibility. Large amounts (up to 28.7 mmol g⁻¹) of ethanol with fuel-grade (99.5 %+) and even higher purities (99.9999 %+) can be produced in a single adsorption process from not only 95 : 5 but also 10 : 90 ethanol/water mixtures. More interestingly, the pore-opening adsorbent possessing large pore apertures showed not only high water adsorption capacity but also exceptionally high water/ethanol selectivity characteristic of molecular sieving. Computational simulations demonstrated the critical role of guest-anchoring aperture for the guest-dominated gating process.     

Peripherally Heavy-Atom-Decorated Strategy Towards High-Performance Pure Green Electroluminescence with External Quantum Efficiency over 40 %

Heavy-atom integration into thermally activated delayed fluorescence (TADF) molecule could significantly promote the reverse intersystem crossing (RISC) process. However, simultaneously achieving high efficiency, small roll-off, narrowband emission and good operational lifetime remains a big challenge for the corresponding organic light-emitting diodes (OLEDs). Herein, we report a pure green multi-resonance TADF molecule BN-STO by introducing a peripheral heavy atom selenium onto the parent BN-Cz molecule. The organic light-emitting diode device based on BN-STO exhibited state-of-the-art performance with a maximum external quantum efficiency (EQE) of 40.1 %, power efficiency (PE) of 176.9 lm W⁻¹, well-suppressed efficiency roll-off and pure green gamut. This work reveals a feasible strategy to reach a balance between fast RISC process and narrow full width at half maximum (FWHM) of MR-TADF by heavy atom effect.     

Self-Accelerating Diels–Alder Reaction for Preparing Polymers of Intrinsic Microporosity

It is a formidable challenge in polycondensation to simultaneously construct multiple covalent bonds to prepare double-stranded polymers of intrinsic microporosity (PIMs) with fused multicyclic linkages. To the best of our knowledge, this is the first study to develop a self-accelerating Diels–Alder reaction for successfully preparing double-stranded PIMs with fused multicyclic backbone structures. A self-accelerating Diels–Alder reaction was developed based on the [4+2] cycloaddition of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DIBOD) and ortho-quinone compounds. In this reaction, the cycloaddition of ortho-quinone with the first alkyne of DIBOD activates the second alkyne, which reacts with ortho-quinone at a rate constant 192 times larger than that of the original alkyne. Using this self-accelerating reaction to polymerize DIBOD and spirocyclic/cyclic difunctional ortho-quinone monomers, a novel stoichiometric imbalance-promoted step-growth polymerization method was developed to prepare PIMs. The resultant PIMs possess intrinsic ultramicropores with pore sizes between 0.45 to 0.7 nm, high specific surface areas above 646 m² g⁻¹, and good H₂ separation performance.     

Switchable Fluorescent Light-Up Aptamers Based on Riboswitch Architectures

Fluorescent light-up RNA aptamers (FLAPs) such as Spinach or Mango can bind small fluorogens and activate their fluorescence. Here, we adopt a switching mechanism otherwise found in riboswitches and use it to engineer switchable FLAPs that can be activated or repressed by trigger oligonucleotides or small metabolites. The fluorophore binding pocket of the FLAPs comprises guanine (G) quadruplexes, whose critical nucleotides can be sequestered by corresponding anti-FLAP sequences, leading to an inactive conformation and thus preventing association with the fluorophore. We modified the FLAPs with designed toehold hairpins that carry either an anti-FLAP or an anti-anti-FLAP sequence within the loop region. The addition of an input RNA molecule triggers a toehold-mediated strand invasion process that refolds the FLAP into an active or inactive configuration. Several of our designs display close-to-zero leak signals and correspondingly high ON/OFF fluorescence ratios. We also modified purine aptamers to sequester a partial anti-FLAP or an anti-anti-FLAP sequence to control the formation of the fluorogen-binding conformation, resulting in FLAPs whose fluorescence is activated or deactivated in the presence of guanine or adenine. We demonstrate that switching modules can be easily combined to generate FLAPs whose fluorescence depends on several inputs with different types of input logic.     

Activatable NIR-II Photothermal Lipid Nanoparticles for Improved Messenger RNA Delivery

Endosomal escape remains a central issue limiting the high protein expression of mRNA therapeutics. Here, we present second near-infrared (NIR-II) lipid nanoparticles (LNPs) containing pH activatable NIR-II dye conjugated lipid (Cy-lipid) for potentiating mRNA delivery efficiency via a s timulus-responsive p hotothermal-promoted e ndosomal e scape d elivery (SPEED) strategy. In acidic endosomal microenvironment, Cy-lipid is protonated and turns on NIR-II absorption for light-to-heat transduction mediated by 1064 nm laser irradiation. Then, the heat-promoted LNPs morphology change triggers rapid escape of NIR-II LNPs from the endosome, allowing about 3-fold enhancement of enhanced green fluorescent protein (eGFP) encoding mRNA translation capacity compared to the NIR-II light free group. In addition, the bioluminescence intensity induced by delivered luciferase encoding mRNA in the mouse liver region shows positive correlation with incremental radiation dose, indicating the validity of the SPEED strategy.