Weigang Lu

We present a crystalline mate strategy for the structure elucidation of hard-to-crystallize indole derivatives through cocrystallization with a strong π-acidic Ag(I) cyclic trinuclear complex (Ag₃). This approach enables the successful supramolecular stacking of the low-π-basic indole derivatives with the Ag₃ complex by leveraging noncovalent interactions such as hydrogen bonding, highlighting the potential of the crystalline-mate strategy for constructing functional cocrystals.

The development of robust, efficient, and recyclable heterogeneous photocatalysts for solar-driven organic synthesis remains a significant challenge. Herein, we report the synthesis of a robust hafnium-based metal-organic framework, JNU-228, by using a donor-acceptor-donor (D-A-D) ligand, 4,4',4″,4‴-(1,4-phenylenebis(1H-imidazole-2,4,5-triyl))tetrabenzoate (PBIT). The integration of photoactive triphenylimidazole units with Hf₆-oxo clusters endows JNU-228 with enhanced visible-light absorption and a suitable band gap. Under visible-light irradiation, JNU-228 efficiently catalyzes the hydroxylation of arylboronic acids and the trifluoromethylation of coumarins and indoles. Moreover, JNU-228 maintains its structural integrity and catalytic activity over multiple cycles. This work demonstrates that incorporating molecular D-A-D photosensitizers into stable MOF matrices is a powerful strategy for developing superior heterogeneous photocatalysts for sustainable organic transformations.

Metal–organic frameworks (MOFs) are promising adsorbents for atmospheric water harvesting (AWH), particularly in arid climates. However, the inherently narrow pores (typically with sizes < 2 nm) of conventional MOFs limit both water diffusion and adsorption capacity, thereby constraining the practical daily water yield of MOF‐based AWH systems. Herein, ordered mesopore engineering is applied to a typical hygroscopic MOF, UiO‐66‐NH ₂ , to construct channels with larger pores, thereby overcoming these limitations. The resulting material with uniform 11 nm 2D hexagonal mesopores, denoted OM‐UiO‐66‐NH ₂ , exhibits a 3.7‐fold faster water adsorption rate and nearly an order‐of‐magnitude higher effective water diffusivity than the pristine UiO‐66‐NH ₂ at 30% relative humidity (RH). Moreover, OM‐UiO‐66‐NH ₂ achieves a 12% increase in water uptake capacity (0.43 g g ⁻¹ at 30% RH) and maintains stable performance over 500 adsorption–desorption cycles. When integrated into a modular harvester, OM‐UiO‐66‐NH ₂ exhibits ultrafast adsorption (92% saturation within 5 min) and high condensation efficiency (94%), achieving a daily water yield of 27.8 L kg ⁻¹ day ⁻¹ at 30% RH. This study demonstrates that ordered mesopore engineering effectively overcomes diffusion limitations in MOFs, advancing the design of high‐performance materials for efficient AWH in arid environments.

Developing robust materials that exhibit full-color, switchable, circularly polarized luminescence (CPL) remains a significant challenge. Herein, we report a facile, one-pot encapsulation of achiral dyes within chiral metal-organic frameworks (MOFs) for tunable CPL emission. This approach leverages the chiral microenvironment of MOFs to transfer chirality to the dye molecules, as evidenced by distinct mirror-image circular dichroism (CD) signals. Notably, the confinement effect not only imparts CPL activity to the guest molecules but also enhances their emission intensity via host-guest energy transfer. By controlling the encapsulation of dyes that emit blue (CBS), green (C6), and red (RB) light, we successfully achieved tunable CPL emission across the entire visible spectrum. Furthermore, optimizing the mass ratio of three trichromatic dyes yielded white-light CPL emission with a CIE 1931 coordinate of (0.30, 0.32) and a dissymmetry factor (g_lum) of |2 × 10^-3|.

A facile, one-pot, and green synthesis of functionalized covalent organic frameworks via ultrasound-assisted multicomponent Doebner reactions in aqueous media.

The practical application of metal-organic frameworks (MOFs) is often hindered by the trade-off among structural stability, synthetic complexity, and functional tunability. Herein, we present a facile in situ modular assembly of highly stable 12-connected Ni₈-MOFs by integrating the formation of covalent imine bonds and metal-ligand coordination bonds in a one-pot reaction. This approach utilizes simple precursors of nickel acetate, 4-aminopyrazoles, and diverse aromatic aldehydes to construct a library of 31 highly crystalline Ni₈-MOFs (JNU-230-JNU-260) under traditional refluxing conditions. We further demonstrate the scalability and sustainability of this synthetic strategy, affording gram-scale production per batch using recycled reaction solvents, with no compromise in crystallinity or porosity for at least 3 additional batches. Moreover, in situ modular assembly and donor-acceptor regulation enable the formation of JNU-244 as a highly efficient and stable heterogeneous photocatalyst, achieving a yield of up to 99% in a visible-light-driven cross-dehydrogenative coupling reaction with excellent recyclability. This work offers a new platform for the precise and sustainable construction of highly stable, functionally advanced MOFs, highlighting the power of synergistic covalent-coordination-dual driven assembly in materials design.

Crystallographic analysis has become the most reliable method for elucidating the chemical structures and absolute configurations of natural products. In this study, we present an in situ acetylation-tagging approach to enable the cocrystallization of difficult-to-crystallize molecules bearing hydroxyl or amino groups with cyclic trinuclear complexes (Ag₃Pz₃). Single crystals are readily obtained upon slow evaporation after adding acetylating reagents and then Ag₃Pz₃ into an NMR tube. This acetylation tagging procedure introduces electron-rich acetyl groups with conformational flexibility that serve as beacons for electron-deficient Ag₃Pz₃, leading to effective π-acid···base supramolecular interactions. Using this NMR tube protocol, we have successfully determined the structures of over 40 difficult-to-crystallize molecules, including flexible long-chain alcohols, macrocyclic alcohols, and aliphatic amines. These molecules, if not acetylated, would not cocrystallize with Ag₃Pz₃. Further applications demonstrate the effectiveness of this protocol in determining the chemical structures and absolute configurations of highly complex natural glycosides and pharmaceutical molecules, showcasing broad substrate compatibility and its potential for analyzing difficult-to-crystallize molecules containing hydroxyl or amino groups.

Efficiently separating acetylene (C ₂ H ₂ ) from carbon dioxide (CO ₂ ) has been a long‐standing challenge due to their similar molecular dimensions and physical properties. Herein, we report a series of isostructural pillar‐layered metal–organic frameworks (MOFs), named JNU‐13, JNU‐13‐CH ₃ , and JNU‐13‐(CH ₃ ) ₂ . These MOFs feature one‐dimensional (1D) channels integrated with orthogonally arrayed side pockets, enabling dense packing of C ₂ H ₂ molecules while maintaining rapid diffusion pathways. Specifically, JNU‐13‐CH ₃ achieves a high C ₂ H ₂ packing density of 360 g L ⁻¹ , a low adsorption enthalpy of 31.61 kJ mol ⁻¹ , and adsorption/desorption coefficients one to two orders of magnitude higher than other benchmark MOFs. Breakthrough experiments reveal a high C ₂ H ₂ capture capacity of 3.46 mmol g ⁻¹ from an equimolar C ₂ H ₂ /CO ₂ mixture at 298 K and 1 bar, even under humid conditions. Moreover, we demonstrate the scale‐up synthesis of JNU‐13‐CH ₃ and gas‐cylinder collection of high‐purity C ₂ H ₂ , achieving >99.9% from a C ₂ H ₂ /CO ₂ (95/5) mixture and >99.7% from a C ₂ H ₂ /CO ₂ /CH ₄ (95/2.5/2.5) mixture. Overall, this study highlights the effectiveness of orthogonal‐arrayed side pockets for balancing dense packing and mass transport, offering a promising strategy for energy‐efficient C ₂ H ₂ purification.