Cheng He

Tumor microenvironment (TME) interactive platforms are promising for accurate diagnostics and therapeutics. Herein, a smart interactive system (G⊂H) consisting of a hypoxia‐acid dual triggered multifunctional guest (G) and an amphipathic metal‐organic capsule (H) was successfully established for bioimaging and treatment. Hydrophobic G is encapsulated in cavity of H to form the homogeneous soluble G⊂H, which enhances its accumulation in tumor cells, controls the interactive regulation between G⊂H and TME, and facilitates the sensitivity of tumor cell therapy. When triggered in TME, G⊂H selectively releases an alkylating agent and a doxifluridine (DFUR) via the activation of azo and ketal linkers for multidrug chemotherapy, and the fluorescence emission from the activated G⊂H is used for real‐time release visualization of the hypoxia‐activating drug in cell substructure and hypoxia imaging. Owing to its homogeneous delivery, TME regulation and TME response properties toward the hypoxia tumor cells, G⊂H exhibits significantly higher toxicity in a hypoxic environment (0.1% O ₂ ) than that in normoxia. As expected, G⊂H performs good imaging capability and treatment effect in hypoxia tumor cells, flow cytometry assay and tumor‐bearing mice, implying its great potential in bioimaging and multidrug synergistic therapy.

CCOFs were obtained by embedding the l -Phe moiety into the skeletal frameworks for the enantiomeric discrimination of amino acids. Additionally, a chiral l -BPHPH-TFP-COF membrane exhibited moderate enantioselective separation performance toward Phe.

A photoactive dinuclear Ir(III)-based amine cage was constructed through dynamic imine assembly followed by reductive fixation. Subsequent post-coordination with Ni(II) ions generated a supramolecular catalytic system that integrates visible-light harvesting with Ni(II)-mediated substrate activation, enabling aerobic α-hydroxylation of β-ketoesters under 450 nm irradiation in up to 88% yield.

Ionic Ir( iii ) cage-confined ultrasmall Au nanoclusters enable substrate sieving and electron relay for visible-light-driven stepwise reduction of nitroarenes to azobenzenes with complete conversion and up to 98% selectivity.

The directional transfer of electrons and hydrogen is of profound importance to the functions of enzymes such as vitamin B12 (VB12), offering bioinspired opportunities to address the pending issues in photocatalysis. Nevertheless, the direct biomimicry of VB12 in artificial catalytic systems remains a significant challenge. Herein, we report the integrated mimicry of the VB12-dependent dehalogenase and photoreceptor protein CarH by designing a luminescent cobalt-dye coordination polymer (CP) with an anisotropic electronic structure and a switchable ligand field. The well-tuned confined excited electrons of the framework enable the directional cascade electron transfers among ligands, nodes, and substrates. The ligand field of cobalt nodes could be modulated via ligand exchange to switch on the activation of cobalt−H sites. These synergistic regulations achieve potent photoreduction of inert substrates and subsequent cobalt−H catalysis, as verified by the hydroarylation probe reaction of aryl olefins with exclusive Markovnikov selectivity. Through directional, multistep translocations of hydrogen/carbon-centered radicals during chain-walking processes, the functionalization of aliphatic olefins is further achieved in a value-added, remote, regiospecific manner. The proposed mechanism is supported by experimental and theoretical density functional theory studies. This work presents a strategy not only biomimicking but also going beyond the natural VB12-enzymes.

Two series of lanthanide ions embedded covalent organic frameworks (COFs), TpThz@Ln and TpBch@Ln (Ln = Tb, Eu, Ce), were obtained by subsequently incorporating the various lanthanide ions into two hydrazone-linked COFs (TpThz and TpBch) via post-synthetic modification, respectively. Structural characterization confirmed that the lanthanide-modified COFs retained crystallinity and structural integrity, with the lanthanide ions uniformly distributed within the framework. The resulting materials were employed as heterogeneous catalysts for the cyanosilylation of aromatic aldehydes with trimethylsilyl cyanide (TMSCN) and the synthesis of 2,3 dihydroquinazolin 4(1H) one derivatives, respectively. Both reactions proceeded efficiently at room temperature, with broad substrate scope and nice functional group tolerance. And the porous structure of the COFs catalysts exhibited size-selectivity toward large substrates. Moreover, the catalysts demonstrated well recyclability. This work provides the COFs containing multidentate coordination sites as the promising platform to immobilize active metal centers for designing heterogeneous catalyts, and highlights the potential of lanthanide ion modified COFs as robust, reusable heterogeneous catalysts for value–added organic syntheses.

The heterogenization of molecular catalysts to be compatible with industrialization demands still faces great challenges. In this work, we demonstrate for the first time that the activity of a molecular catalyst is unrestricted when installed in nanostructured coordination polymers (CPs). CPs that can be used to obtain ultrafine nanowires by ultrasound exfoliation are extremely limited. We illustrate that chain-like CPs can be designed using electrostatic ligand-capped low-coordination-number metal ions and electropositive ligands as building blocks. This guides the preparation of the three-dimensional (3D) chain-like CPs from chloride ion-capped Cu-based chromophores and 1,1'-(1,4-phenylenebis(methylene))bis(3-carboxy quinolin-1-ium) chloride; subsequently, ultrafine sub-1 nm nanowires were obtained via ultrasound exfoliation. The formed ultrafine sub-1 nm CP nanowires demonstrate high activity enhancement for functionalization of C(sp³)-H bonds with conversion being significantly increased for alkylation, thiolation, and oxidation of C(sp³)-H bonds after exposure to external surfaces of the flexible nanowires. Therefore, the observed activity increases in the order CuCl₂ < bulk CP crystals < CP nanowires in functionalization of C(sp³)-H bonds. This work not only provides a strategy for constructing chain-like CPs and their ultrafine nanowires but also paves the way for expanding the diversity of the ultrafine 1D CP nanowires.

Enantioselective recognition is pivotal in chemical biology and pharmaceutical science, yet achieving high-fidelity discrimination remains challenging. Drawing inspiration from natural helical architectures that create stereospecific microenvironments, we report a class of homochiral dinuclear Ir(III) metallohelices as modular building units for porous crystalline frameworks. The Λ₂S₆-DP and Δ₂R₆-DP metallohelices, assembled from enantiopure 1,2-diphenylethylenediamine (DPEN, RR- or SS-form) spacers and spatial-matching aldehyde-terminated fac-Ir(ppy)₃ (Δ- or Λ-handed) vertices, organize into well-defined chiral channels through stereoregular C-H···π and aromatic stacking. These confined microenvironments cooperate with the intrinsic phosphorescence of Ir(III) centers to enable highly enantioselective sensing. The Λ₂S₆-DP framework exhibits distinct recognition for R-BINOL and D-Trp, with enantiomeric factors (EF) reaching 6.09 and 5.54, respectively, while its enantiomeric Δ₂R₆-DP counterpart shows the reversed preference. Crucially, replacing the spacer with a methoxy-substituted analogue disrupts the π-stacking network and erases enantiodiscrimination, confirming the essential role of aromatic-driven assembly in creating functional chiral spaces. This work establishes a modular strategy for constructing phosphorescent chiral microenvironments by organization of homochiral photoactive metallohelices that effectively discriminate enantiomers through differential phosphorescence response.

Partial oxidation of alkanes with green O ₂ source for valuable oxygenated products is one of the most challenging tasks in chemistry due to the difficulty of the activation of both inert C(sp ³ )─H bonds and unreactive O ₂ molecules. Taking advantage of the structural designability of covalent organic frameworks (COFs) for incorporating diverse functional groups and embedding redox‐active Fe/Cu ions into a bipyridine‐based COF ( BPY‐COF ), metalated COFs ( M@COF s; M = Fe, Cu) with open coordinative metal sites are obtained as heterogeneous photocatalysts for the activation and aerobic oxidation of alkanes under mild conditions. Photoinduced activation of the C(sp ³ )–H bonds is achieved via hydrogen atom transfer (HAT) by chlorine radicals ( Cl •), which are generated via ligand‐to‐metal charge transfer (LMCT) between the metal centers in the M@COF s and chlorine ions; and the M@COF s with good photoelectric performance can activate O ₂ via photoinduced electron transfer (PET). Through dynamic matching of the photoinduced C–H bond and oxygen activation processes, a highly efficient partial oxidation transformation of alkanes is achieved. This study paves the way for the application of multifunctional COF materials in energy and chemical feedstock‐related fields.