Mingyan Wu

Employing the epimeric ligands, cinchonidine (L1) and cinchonine (L2), two chiral Cu(I) coordination polymers were synthesized: a 1D chain Cu4I4(L1) and a 3D framework Cu4I4(L2). Structural analyses reveal that Cu4I4(L1) incorporates interconnected distorted gyroscope-like and cubane-type Cu4I4 clusters, whereas Cu4I4(L2) comprises solely cubane-type Cu4I4 clusters. This architectural divergence could be attributed to the distinct spatial preferences of the two N-donor atoms in the epimeric ligands. Photoluminescence studies show that Cu4I4(L1) emits orange light with a single broad band (λem = 614 nm, ΦPL = 21.03%), while Cu4I4(L2) displays yellow emission consisting of multiple bands (λem = 575 nm, ΦPL = 1.32%). DFT calculations correlate these differences to the variations in frontier orbital distributions and electronic transition pathways. Notably, the two compounds exhibit distinct circularly polarized luminescence with maximum glum values of +6.1 × 10–3 for Cu4I4(L1) and –2.4 × 10–3 for Cu4I4(L2). This work illustrates how subtle stereochemical differences in epimeric ligands direct the structural self-assembly of chiral Cu(I)-cluster-based coordination polymers, thereby tuning their photophysical and chiroptical properties, and provides a valuable guideline for designing CPL-active Cu(I)-cluster-based materials.

One‐step purification of C ₂ H ₄ from a C ₂ H ₂ /CO ₂ /C ₂ H ₄ mixture represents a significant industrial challenge. However, conventional ligand engineering strategies struggle to simultaneously enhance adsorption capacity and separation selectivity. Herein, we present an innovative “two‐in‐one” anion engineering strategy involving the substitution of SiF ₆ ²⁻ with ZrF ₆ ²⁻ , which enhances CO ₂ capture while effectively shields C ₂ H ₄ adsorption at the fluorine sites. Compared to SIFSIX‑1‑Cu‑(CH ₃ ) ₂ , ZrFSIX‑1‑Cu‑(CH ₃ ) ₂ exhibits a dramatically enhanced CO ₂ uptake (from 35.3 to 87.3 cm ³ /g). More importantly, the adsorption preference shifts from C ₂ H ₄ ‐selective to CO ₂ ‐selective, with the CO ₂ /C ₂ H ₄ (50/50) ideal adsorbed solution theory (IAST) selectivity increasing from 0.59 to 1.66. Dynamic breakthrough experiments demonstrate the exceptional separation performance of ZrFSIX‑1‑Cu‑(CH ₃ ) ₂ for a C ₂ H ₂ /CO ₂ /C ₂ H ₄ (1/9/90) mixture. Theoretical calculations reveal that the highly electronegative F atoms on the ZrF ₆ ²⁻ anions enhance the interactions with CO ₂ , while ligand rotation‐induced pore contraction and methyl steric effects act synergistically to hinder C ₂ H ₄ from accessing the fluorine sites. This study provides a new paradigm for the design of materials aimed at purifying C ₂ H ₄ from multi‐component mixtures.

One‐step purification of C ₂ H ₄ from a C ₂ H ₂ /CO ₂ /C ₂ H ₄ mixture represents a significant industrial challenge. However, conventional ligand engineering strategies struggle to simultaneously enhance adsorption capacity and separation selectivity. Herein, we present an innovative “two‐in‐one” anion engineering strategy involving the substitution of SiF ₆ ²⁻ with ZrF ₆ ²⁻ , which enhances CO ₂ capture while effectively shields C ₂ H ₄ adsorption at the fluorine sites. Compared to SIFSIX‑1‑Cu‑(CH ₃ ) ₂ , ZrFSIX‑1‑Cu‑(CH ₃ ) ₂ exhibits a dramatically enhanced CO ₂ uptake (from 35.3 to 87.3 cm ³ /g). More importantly, the adsorption preference shifts from C ₂ H ₄ ‐selective to CO ₂ ‐selective, with the CO ₂ /C ₂ H ₄ (50/50) ideal adsorbed solution theory (IAST) selectivity increasing from 0.59 to 1.66. Dynamic breakthrough experiments demonstrate the exceptional separation performance of ZrFSIX‑1‑Cu‑(CH ₃ ) ₂ for a C ₂ H ₂ /CO ₂ /C ₂ H ₄ (1/9/90) mixture. Theoretical calculations reveal that the highly electronegative F atoms on the ZrF ₆ ²⁻ anions enhance the interactions with CO ₂ , while ligand rotation‐induced pore contraction and methyl steric effects act synergistically to hinder C ₂ H ₄ from accessing the fluorine sites. This study provides a new paradigm for the design of materials aimed at purifying C ₂ H ₄ from multi‐component mixtures.

Developing hydrogen‐bonded organic frameworks (HOFs) for highly efficient Xe/Kr separation is an attractive alternative for producing high‐purity noble gases. However, its practical application is hampered by insufficient binding sites and intrinsically slow adsorption kinetics. We herein report a microporous HOF (HOF‐TBPDM) featuring the unique two‐dimensional (2D) and size‐matched pore architecture, which enables the rapid diffusion of Xe and high‐efficiency Xe/Kr separation. Specifically, HOF‐TBPDM achieves a high Xe uptake and a record Xe/Kr IAST selectivity (26.9) at 298 K and 1 bar. Especially, the kinetic adsorption results confirm the 2D pores lead to the rapid Xe diffusion rate. Dynamic breakthrough experiments indicate that after one cycle of separation operation 4.8 mol kg ⁻¹ high‐purity Kr (>99.99%) and 1.0 mol kg ⁻¹ Xe (>99.9%) can be directly obtained. The dynamic selectivity calculated from desorption process is as high as 16.5, which exceeds all the reported porous organic materials. Gas‐loaded crystal data combined with molecular modeling clearly reveal that the size‐matched pores within HOF‐TBPDM induce a stronger polarization effect on Xe than Kr, leading to preferential binding of Xe molecules. Overall, this study demonstrates the effectiveness of 2D pore in HOFs for balancing thermodynamic adsorption and kinetic diffusion, providing a viable strategy for advanced Xe/Kr separation.

Developing hydrogen‐bonded organic frameworks (HOFs) for highly efficient Xe/Kr separation is an attractive alternative for producing high‐purity noble gases. However, its practical application is hampered by insufficient binding sites and intrinsically slow adsorption kinetics. We herein report a microporous HOF (HOF‐TBPDM) featuring the unique two‐dimensional (2D) and size‐matched pore architecture, which enables the rapid diffusion of Xe and high‐efficiency Xe/Kr separation. Specifically, HOF‐TBPDM achieves a high Xe uptake and a record Xe/Kr IAST selectivity (26.9) at 298 K and 1 bar. Especially, the kinetic adsorption results confirm the 2D pores lead to the rapid Xe diffusion rate. Dynamic breakthrough experiments indicate that after one cycle of separation operation 4.8 mol kg ⁻¹ high‐purity Kr (>99.99%) and 1.0 mol kg ⁻¹ Xe (>99.9%) can be directly obtained. The dynamic selectivity calculated from desorption process is as high as 16.5, which exceeds all the reported porous organic materials. Gas‐loaded crystal data combined with molecular modeling clearly reveal that the size‐matched pores within HOF‐TBPDM induce a stronger polarization effect on Xe than Kr, leading to preferential binding of Xe molecules. Overall, this study demonstrates the effectiveness of 2D pore in HOFs for balancing thermodynamic adsorption and kinetic diffusion, providing a viable strategy for advanced Xe/Kr separation.

Spherical surfactant micelles, widely used as templates for synthesizing porous inorganic materials, suffer from undeterminable atomic-level structures. Developing structurally precise spherical micelle-like architectures is therefore highly beneficial for understanding template syntheses yet remains challenging. Here, we demonstrate a series of micelle-like π-stacked architectures self-assembled from tripodal synthons ([ML(SO₄)], [ML(SCN)]⁺, or [H₃L(HPO₄)]⁺, where M = Co²⁺ or Zn²⁺ and L = tris(2-benzimidazolylmethyl)amine). These structures form through anion-coordination-regulated π-π stacking. While a honeycomb architecture of oppositely aligned neutral [CoL(SO₄)] forms without the directing of anions, various cationic micelle-like π-stacked architectures of [ML(SCN)]⁺ and [H₃L(HPO₄)]⁺ are successfully constructed via anion coordination-regulated π-π stacking. Within these assemblies, the π-stacked tripodal synthons and the H-bonded anion networks mutually template each other, reminiscent of how surfactant micelles template porous inorganic materials. Remarkably, this approach yields two new Frank-Kasper (FK) C15 phases, representing the first FK C15 complexes formed by small-molecule assembly. These results establish a universal strategy leveraging the interplay between π-π stacking and anion coordination to access complex supramolecular FK structures, potentially enabling new synthetic approaches for porous inorganic materials such as zeolites and porous silicon.