Terpyridine ligands have been applied as a class of unique ligands due to their rich coordination chemistry in the catalysis. Herein, we developed a new class of C ₂-symmetric chiral terpyridine-pyrroloimidazolone ligands (TPy-BPI). Their catalytic activity was evaluated in the asymmetric Friedel-Crafts alkylation of indoles with 2, 3-dioxopyrrolidines. Excellent yields (up to 92%) and high enantioselectivities (up to 97% ee) are obtained for a wide range of substrates under mild conditions. In addition to 2, 3-dioxopyrrolidines, β, γ-unsaturated α-ketoesters were also compatible in the Ni(OTf) ₂-TPy-BPI ligand L1-catalyzed reaction. Control experiments, single crystal structure of two TPy-BPI L1-Ni(OTf) ₂ complexes, and DFT calculations revealed the origins of the enantioselectivity. To the best of our knowledge, our work is the first report showing that the terpyridine framework contained only two nitrogen atoms coordinating with the metal, and the additional pyridine unit only acted as stereodirecting element, which is different from the previously reported terpyridine ligands containing all three nitrogen atoms coordinating with the metal.

Triple interlocked systems represent highly intricate topological structures, formed by entwining two mechanically interlocked cages. Achieving controlled and straightforward construction of these aesthetic topologies continues to pose an enduring challenge. Herein, we employ a coordination-driven self-assembly strategy, capitalizing on non-covalent interactions in conjunction with half-sandwich metal units and meticulously designed isoquinoline-based ligands, to achieve the effective construction of organometallic interlocked cages 1 and 2. The resulting triple interlocked system’s formation and architecture were validated by single-crystal X-ray diffraction, electrospray ionization mass spectroscopy, and comprehensive NMR tests. The Independent Gradient Model (IGM) more intuitively demonstrates the multiple stacking interactions within cage compounds, while planarity analysis elucidates the self-adaptability of the ligands and their tunable conformations.

Due to the extremely similar physical and chemical properties of C ₂H ₆, C ₂H ₄, and C ₂H ₂, purifying ethylene from the C ₂ ternary mixture in one-step is very challenging. In this work, we developed a series of pillar-layered MOF materials ((Ni(BTC)(Bipy), Ni(BTC)(3-Me-Bipy), and Ni(BTC)(3-NH ₂-Bipy)) through the functionalization of pillar ligands using pore engineering strategies. Single-component adsorption isotherm measurements demonstrate that these materials preferentially adsorb C ₂H ₆ and C ₂H ₂, thereby achieving one-step purification of the three C ₂ hydrocarbons to obtain C ₂H ₄. By introducing functional groups on the pillars, the selectivity for C ₂H ₆/C ₂H ₄ increased by over 10%, while the selectivity for C ₂H ₂/C ₂H ₄ increased by more than 300%. Specifically, Ni(BTC)(3-NH ₂-Bipy) exhibits a selectivity of 1.5 for C ₂H ₆/C ₂H ₄ (50/50, V/ V) and 5.16 for C ₂H ₂/C ₂H ₄ (1/99, V/ V). Under ambient conditions, the adsorption capacity of Ni(BTC)(3-NH ₂-Bipy) for C ₂H ₂ reached 121.6 cm ³/g, Ni(BTC)(3-NH ₂-Bipy) exhibits superior C ₂H ₂ adsorption capacity and C ₂H ₂/C ₂H ₄ selectivity compared to many classic materials, including TJT-100, Azole-Th-1, and MOF-808-Bzz, commonly used for C ₂H ₄ purification from C ₂ ternary mixtures. Dynamic breakthrough experiments indicate that in a ternary C ₂ mixture, Ni(BTC)(3-NH ₂-Bipy) preferentially captures C ₂H ₆ and C ₂H ₂, enabling one-step purification of C ₂H ₄.

Herein, a [1, 2]-phospha-Brook rearrangement-initiated palladium-catalyzed cyclization reaction for base-controlled selective synthesis of 2 H-isoindole-1-carboxamide and 2 H-isoindole-1-carbonitrile derivatives has been described. This strategy features double isocyanide insertion, efficient bond combinations, simple operation and reaction conditions. Mechanistic studies show that the [1, 2]-phospha-Brook rearrangement is the key step in this reaction. This protocol offers a novel and concise strategy for the synthesis of 2 H-isoindole derivatives.

We synthesized a dialane(4) compound ( 2) stabilized by double-layer N-P ligands. Upon reduction with KC ₈, compound 2 demonstrates solvent-dependent reactivity: in THF, it undergoes C—O bond cleavage to yield product [MeN(CH ₂CH ₂NPiPr ₂) ₂Al(CH ₂) ₄O] ₂K ₂; whereas in a THF/toluene mixture, it results in the activation of the methyl C—H bond in toluene, forming product [MeN(CH ₂CH ₂NPiPr ₂) ₂AlH] ₂K ₂. We propose that these reactions involve an “Al(I)” intermediate, which facilitates oxidative addition with either the C—O bond of THF or the C—H bond of toluene.

The construction of luminescent two-dimensional (2D) imine-linked covalent organic frameworks (COFs) is a formidable challenge due to the strong interlayer stacking and bond rotations that typically suppress intramolecular charge transfer (ICT), leading to nonradiative energy dissipation. Herein, three COFs with tailored interlayer distances and bond rotations are designed to modulate the ICT behaviours. The targeted COF (TPAZ-TPE-COF) achieved a significantly enhanced photoluminescence quantum yield (PLQY) of 21.22% in the solid state by restricting bond rotation and enlarging the layer distance. This represents a 3.5-fold and 530.5-fold improvement over TPAZ-PYTA-COF (6.15%), which has a shortened interlayer space, and TPAZ-PATA-COF (0.04%), which exhibits strong bond rotations, respectively. Importantly, TPAZ-TPE-COF also exhibits exceptional sensing performance for iron ions, with a detection limit at the ppb level. Both experimental and theoretical analyses reveal that the prominent luminescent performance of TPAZ-TPE-COF is assigned to the effective suppression of nonradiative pathways, especially those arising from interlayer stacking and bond vibrations. These findings pave the way for deliberate construction of imine-linked 2D COFs with high PL intensity, thereby expanding the portfolio of luminescent COFs with potential applications in sensing and optoelectronics.

The power conversion efficiencies (PCEs) of non-fullerene acceptor (NFA)-based organic solar cells (OSCs) have undergone an exciting development in recent years, but the poor intrinsic stability of exocyclic ethylene bridges in NFAs poses a significant challenge to their commercialization. In this work, we propose a new pyran-locking strategy that can stabilize the exocyclic ethylene bridge connecting the strong electron-deficient 2-(3-oxo-2, 3-dihydroinden-1-ylidene)malononitrile end group, based on which two dimerized NFAs (ITBIC-F and TBTBIC-F) with an A-D-π-A-π-D-A structure have been successfully synthesized with significantly improved chemical and photochemical stabilities in comparison with traditional NFAs without the ring-locked structure. The ITBIC-F and TBTBIC-F -based OSCs not only achieve promising PCEs of 13.03% and 10.01%, respectively, but also show good device stability; the ITBIC-F-based unencapsulated devices can retain 75% and 62% of their initial PCEs, respectively, under continuous heat (85°C) and light irradiation (LED, 100 mW·cm ^–2) in a nitrogen atmosphere.

Comprehensive Summary: Natural products with high oxidation states and complex chemical skeletons exhibit diverse bioactivities due to their unique interactions with biological targets. The high oxidation state is characterized by the presence of multiple oxygen-containing functional groups such as hydroxyl groups, carbonyl groups, and epoxides that are usually tough to construct selectively. In recent years, thanks to the development of efficient strategies and sophisticated methodologies, significant advancements have been made in the total syntheses of highly oxidized natural products (HONPs). In this review, we highlight recent examples of HONPs focusing on tetrodotoxin (TTX) and its derivatives, steroidal alkaloids, sesquiterpenes, and diterpenoids since 2019.

Key Scientists: In 2005, the Yang group applied the thioureas as ligands in the Pauson−Khand reaction for total synthesis of triterpene natural products. The methodological advances have achieved total syntheses of a series of topologically complex natural products with diverse structural features in the following years. In 2009, the Baran group established a pioneering “two-phase” approach for the total synthesis of highly oxidized terpenes, an innovative strategy has since inspired numerous advancements in the field. In 2011, Xu and Theodorakis achieved the total synthesis of (−)-jiadifenolide, a highly oxidized sesquiterpene from Illicium. In 2012, the Li group applied 6π electrocyclization for total synthesis of natural products containing aromatic rings. In 2014, the Inoue group introduced the α-alkoxy bridgehead radical, facilitating a unified total synthesis of ryanodane diterpenoids. In subsequent years, radical-based convergent strategies were employed for assembling HONPs. The Li group developed the type ΙΙ [5+2] reaction, which can be efficiently applied in the total synthesis of HONPs featuring bridged ring systems. The Reisman group presented the oxidation pattern analysis that guided their synthetic designs for the synthesis of complex, highly oxidized ryanodane and isoryanodane diterpenes. In 2017, the Gao group reported a photoenolization/Diels-Alder (PEDA) reaction for constructing related polycyclic rings with elevated oxidation states. In 2018, the Ding group developed an unprecedented oxidative dearomatization-induced (ODI) [5+2] cycloaddition/pinacol- type 1, 2-acyl migration cascade to assemble the highly oxygenated bicyclo[3.2.1]octane ring system, which was subsequently applied to the synthesis of highly oxidized grayanane diterpenoids. In the same year, the Gui group explored “bioinspired” strategic transformations that enabled the rapid construction of core framework of steroid and terpenoid natural products. In 2020, the Luo group successfully synthesized several HONPs, including (−)-batrachotoxinin, (−)-zygadenine, and grayanane diterpenoids, employing elegant strategies. In 2021, the Zhang group developed site-specific photochemical desaturation and late-stage skeletal reorganization strategies, enabling the divergent total synthesis of Illicium sesquiterpenes. In 2022, the Jia group achieved the first total synthesis of (−)-principinol C, subsequently accomplished six highly oxidized grayanane diterpenoids. More recently, the Trauner group reported a concise synthesis of tetrodotoxin, employing a particularly elegant strategy.

Comprehensive Summary: Artificial cell wall (ACW) referring to active functional cellular nano-coatings is capable of providing more cell-shell synergic and cooperative properties than conventional single cell nanoencapsulation (SCNE). With the development of SCNE, the issues of cytocompatibility, degradability,etc., have already been improved successively. However, the further emphasis on the cooperativity between the cell itself and its shell is still missing and paying more attention on the functions of cellular hybrids. Recent research proved that the construction of nano-coating on cells not only needs to satisfy the functionalization of the single cells, but also is necessary to empower cells to interact with other cells and environments. This indicates that SCNEs on cells are tending to be more “active” to participate in the metabolic process of cells and gradually develop to the stage of ACWs. This review provided a reasonable description of artificial cell wall, and the realization of this concept requires cooperativity, self-adaption and fluxionality. Then, the methodologies of constructing ACWs were discussed. Finally, the applications were summarized accompanied by the potential outlook in the given fields.

Key Scientists: Within recent ten years, fabricating a biocompatible nano-coating on the surface of cells for cyto-protection rapidly developed. For example, Rawil F. Fakhrullin and Yuri M. Lvov developed a ‘layer-by-layer’ strategy to construct ‘face-lifting’ on the surface of micro-organisms. Afterwards, Choi introduced the concept of ‘artificial spore’ which is thin and tough biocompatible cell encapsulations. At the same time, Tsukruk summarized the functions of hydrogel-based ‘artificial spore’ in terms of cyto-protection in 2013. In 2016, Tang reported that the strategy of biomimetic mineralization can be used to improve and modify the metabolism processes of cells. More advanced, Qu and Hawker separately developed a way to introduce manganese dioxide nanozymes and in-situ-grafting polymers on the surface of cells to realize the responsive effects towards the artificial regulation in 2017. In 2018, Huang showed a way to generate a type of heritable artificial cell wall based on in situ self-assembly of coacervate micro-droplets around yeast cells. In 2019, Jeffrey reported that nanoparticles can be adopted to construct exoskeletons outside the cells which can endow new functions and forming ‘supracells’. Choi put forward the concepts of ‘active shell’ and ‘dynamic shell’ which indicated that the research of cellular nanoencapsulations was beginning to transition to control the fate of cells. Huang introduced a reasonable strategy in constructing degradable artificial cell walls in 2020 and adopted an intracellular mineralization method to regulate metabolic processes of algae to promote hydrogen production. Based on his previous research, this review focused on introducing the fabrication and applications of ‘artificial cell wall’.