Key Takeaways & Executive Findings
- •• • Dimensional evolution from 1D/2D to 3D HMOFs achieved by tuning auxiliary ligand connectivity, yielding a novel 4-(3,3,3,6)-connected topology with heart-shaped channels, enabling dual functionality. • • P/M-HMOF-5 exhibit acid-base bifunctional heterogeneous catalysis for 2,3-dihydroquinazolinone synthesis with excellent yields of 90%–98%, demonstrating high efficiency and potential for industrial fine chemical production. • • M-HMOF-5 shows highest enantioselective fluorescent sensing for phenylalanine with KBH(D-Phe)/KBH(L-Phe) = 5.85, and for D-Phe recognition, KBH(M)/KBH(P) = 7.17, underscoring superior chiral discrimination for analytical applications. • • The integration of catalytic and sensing functions within a single chiral platform, derived from identical chiral building blocks, offers a rational strategy for designing multifunctional materials, reducing processing steps and material costs.
Abstract
The deliberate control of framework dimensionality represents a powerful yet underexplored strategy for tailoring the functionality of homochiral metal-organic frameworks (HMOFs). Herein, we report a logical dimensional evolution from 1D and 2D to 3D HMOFs, achieved by tuning the connectivity of the auxiliary ligand. Employing a planar, three-connected ligand, 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (Tpt), together with enantiopure tetracarboxylate of cyclohexane diamide linkers ((1R,2R/1S,2S)-cyclohexane-1,2-dicarbonyl bis(azanediyl)diisophthalate) (R,R/S,S-CHCAIP) and Zn2+ salts, a pair of 3D porous HMOFs (P/M-HMOF-5) was successfully constructed. The 3D framework features unique heart-shaped channels and a novel 4-(3,3,3,6)-connected topology. Structural analyses reveal trinuclear Zn3(μ3-O) clusters that, upon activation, generate open metal sites. These Lewis acid sites, synergizing with Lewis basic sites from the framework, confer efficient acid-base bifunctional heterogeneous catalysis for the synthesis of 2,3-dihydroquinazolinones in excellent yields (90%–98%). Furthermore, P/M-HMOF-5 serve as highly sensitive and enantioselective fluorescent sensors for amino acids and α-hydroxy carboxylic acids, with the highest discrimination observed for phenylalanine (KBH(D-Phe)/KBH(L-Phe) = 5.85 for M-HMOF-5). This work demonstrates how rational ligand connectivity steers dimensional evolution, enabling the integration of distinct catalytic and sensing functions within a single chiral platform, thereby providing a blueprint for the design of advanced multifunctional materials.
1. Introduction
The profound influence of dimensionality on material properties is exemplified by carbon allotropes, where 3D diamond, 2D graphene, and 1D carbon nanotubes exhibit distinct characteristics and applications. This structure-property relationship has motivated intense interest in dimensional control across material systems. Metal-organic frameworks (MOFs) can be precisely assembled from metal ions/clusters and organic linkers to form 1D nanotubes, 2D nanosheets, and 3D nanocavities. However, research has been underexplored, predominantly focusing on structural description. The deliberate control over MOF dimensionality to manipulate functional properties remains a challenge.
The significance of chirality in pharmaceuticals and biological systems underscores the need for advanced chiral solid-state materials. Homochiral metal-organic frameworks (HMOFs) have emerged as promising platforms due to their well-defined structures, tunable porosity, and tailorable functionality. Current studies have concentrated on intrinsic factors such as chiral secondary building units, electronic/energy transfer, and host-guest interactions. This work addresses the bottleneck by demonstrating how rational ligand connectivity steers dimensional evolution from 1D/2D to 3D HMOFs, enabling the integration of distinct catalytic and sensing functions within a single chiral platform, thus providing a blueprint for designing advanced multifunctional materials.
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Yan-Wu Zhao, Sheng-Yan Zhu, Zhi-Hang Li, Xiao-Jian Han, Nan Zhang, Mei Pan, Xian-Ming Zhang (2026). Dimensionally Extended Homochiral Metal-Organic Frameworks for Catalysis and Enantioselective Sensing. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-4046-6
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Frequently Asked Questions
What is the structural basis for the dimensional evolution from 1D/2D to 3D HMOFs, and how does the auxiliary ligand connectivity influence the final topology?
The dimensional evolution is achieved by tuning the connectivity of the auxiliary ligand Tpt. In the presence of enantiopure tetracarboxylate linkers and Zn2+ salts, the planar three-connected Tpt ligand facilitates the formation of a 3D framework with a novel 4-(3,3,3,6)-connected topology, featuring trinuclear Zn3(μ3-O) clusters and heart-shaped channels. This contrasts with lower-dimensional structures formed with different ligand connectivities, demonstrating that ligand connectivity is a critical structural determinant.
How do the open metal sites and Lewis basic sites in P/M-HMOF-5 contribute to the catalytic activity in the synthesis of 2,3-dihydroquinazolinones?
Upon activation, the trinuclear Zn3(μ3-O) clusters generate open metal sites that act as Lewis acids, while the framework provides Lewis basic sites. This acid-base bifunctionality synergistically catalyzes the synthesis of 2,3-dihydroquinazolinones, achieving excellent yields of 90%–98%. The cooperative effect enhances reaction efficiency and selectivity, making the material a promising heterogeneous catalyst.
What are the key performance metrics for enantioselective sensing of amino acids and α-hydroxy carboxylic acids by M-HMOF-5?
M-HMOF-5 exhibits the highest discrimination for phenylalanine with a binding constant ratio KBH(D-Phe)/KBH(L-Phe) = 5.85. For D-Phe recognition, the ratio KBH(M)/KBH(P) = 7.17, indicating superior chiral sensing of the M-configuration. These metrics demonstrate high sensitivity and enantioselectivity, making the material suitable for analytical detection of chiral biomolecules.
What is the industrial relevance of integrating catalytic and sensing functions in a single HMOF platform?
Integrating catalytic and sensing functions in a single material reduces the need for multiple processing steps and separate materials, lowering costs and improving efficiency. The high catalytic yields (90–98%) and enantioselective sensing capabilities (e.g., KBH ratio 5.85) make P/M-HMOF-5 attractive for applications in pharmaceutical synthesis and chiral analysis, where both functions are often required sequentially.
How does the dimensional evolution strategy compare to other approaches for designing multifunctional chiral materials?
Unlike approaches that focus solely on chiral SBUs or host-guest interactions, this strategy uses rational ligand connectivity to control dimensionality, enabling the integration of distinct functions within a single framework. This provides a more systematic and tunable approach, as demonstrated by the successful construction of 3D HMOFs with both catalytic and sensing capabilities, offering a blueprint for future material design.
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