Supramolecular Framework Research Articles

Elucidating the Microenvironment Structure‐Activity Relationship of Cu Single‐Site Catalysts via Unsaturated N,O‐Coordination for Singlet Oxygen Production

AbstractUnderstanding the microenvironment structure‐activity relationship of singlet‐atom catalysts (SACs) is imperative for the development of high‐performance photocatalytic devices. However, the challenge remains to finely regulate the coordination microenvironment of SACs. Herein, single‐atom Nx─Cu─O4‐x (x = 1–4) photocatalysts with different coordination environments are successfully prepared based on pre‐design reticular supramolecular covalent organic frameworks (COFs) for direct photocatalytic 1O2 production from O2. The results show that the high activity of Cu SACs is closely related to the N,O‐coordination microenvironment, which is primarily ascribed to the different electrophilicity of the N, O atom. The electron configuration of N3‐Cu‐O1 endows photocatalyst enhanced charge transfer capability and the nearest D‐band center to the Fermi level. The “end‐on” type adsorption configuration of O2 at the N3─Cu─O1 active site can promote the breaking of Cu─O bonds rather than O─O bonds. As a result, the N3‐Cu‐O1@COF photocatalyst exhibits the most optimal formation and desorption energies for intermediates •OOH, which provides an advantageous reaction pathway with fewer steps and a lower barrier for 1O2 production. This work highlights the structure‐activity relationship of SACs for long‐term applications.

A Supramolecular Organic Framework‐Mediated Electrochemical Strategy Achieves Highly Selective and Continuous Uranium Extraction

AbstractThe integration of selectivity and electron transfer ability remains a primary challenge in developing electrode materials for uranium electroextraction. Herein, a phenanthroline‐based supramolecular organic framework (MPSOF) is elaborately constructed as a pioneering cathode material through the hydrogen bond‐driven self‐assembly of melamine and 1,10‐phenanthroline 2,9‐dicarboxylic acid (PDA) for selective and continuous electrochemical uranium extraction (EUE). PDA moieties selectively capture UO22+, while the hydrogen bond‐supporting frameworks provide an efficient electron transfer channel for the redox of UO22+. These structural features enable the rapid formation and spontaneous shedding of uranium precipitate from MPSOF, allowing for the regeneration of the selective adsorption sites. As a result, MPSOF‐mediated EUE exhibits a high extraction capacity of 7311 mg U g−1 at a low voltage of −3.5 V but does not reach equilibrium. Cyclic EUE is employed to uranium extraction from simulated high‐salt radioactive effluents and attains high selectivity for uranium. The electroextraction mechanism is confirmed, wherein uranium species transform into (UO2)O2·4H2O. This work not only provides an efficient electrode material for uranium electroextraction, but also presents a novel electrochemical strategy for separation and adsorption of other radionuclides and contaminant ions.

Three robust luminescent Cd(II) coordination polymers as multi-responsive fluorescent sensors for Cu2+, Hg2+, levofloxacin, and acetylacetone in water

Employing coordination polymers (CPs) developing effective organic contaminants and heavy metal ions luminescent detection systems is an ongoing challenge. Three ternary Cd(II) CPs namely [Cd(MIP)(L)0.5(H2O)]n (1), [Cd2(TPA)2(L)(H2O)]n (2), and [Cd2(DCTP)2(L)(H2O)]n (3), (L = 1,6-bis(2-((1H-imidazol-1-yl)methyl)-1H-benzo[d]imidazol-1-yl)hexane, H2MIP = 5-methylisophthalic acid, H2TPA = terephthalic acid, and H2DCTP = 2,5-dichloroterephthalic acid) containing new L ligands, were hydrothermally synthesized and characterized. 1 displays a (4,4)-connected 4,4L28 layer and further extended into the 3D supramolecular framework via π−π stacking interactions. 2 exhibits a (4,4,5)-connected trinodal network with the point symbol of {42.5.62.8}{42.52.72}{42.53.62.73}2. 3 takes on a (3,5,6)-connected framework with the point symbol {3.42.52.7}{3.82}2{33.44.5.62.82.92.10}2. 1 − 3 show highly good thermal stability, and highly acid-base tolerance. The limits of detection (LOD) of 1 − 3 were calculated as follows: for Cu2+, the LODs are 8.92 × 10−8, 5.74 × 10−7, and 9.37 × 10−8 mol L−1, respectively; for Hg²⁺, the LOD values are 3.73 × 10−7, 5.22 × 10−7, and 8.45 × 10−7 mol L−1, respectively. Regarding levofloxacin (LEV), the LODs for 1 − 3 were found to be 5.11 × 10−8 mol L−1, 2.45 × 10−8 mol L−1, and 8.54 × 10−8 mol L−1, respectively. Finally, for acetylacetone (acac), the LODs of 1 − 3 are 5.53 × 10−6, 5.66 × 10−6, and 1.23 × 10−6 mol L−1, respectively. 1 − 3 represent the first examples of exceptional multi-responsive sensing platforms for the detecting of Cu2+, Hg2+, LEV, and acac with high sensitivity, outstanding anti-interference abilities, and low LODs. The possible sensing mechanisms were investigated in detail.

Antitumor Therapy through Photothermal Performance Synergized with Catalytic Activity Based on the Boron Cluster Supramolecular Frameworks.

Chemodynamic therapy (CDT) has received widespread attention as a tumor optical treatment strategy in the field of malignant tumor therapy. Nonmetallic multifunctional nanomaterials as CDT agents, due to their low toxicity, long-lasting effects, and safety characteristics, have promising applications in the integrated diagnosis and treatment of cancer. Here, we modified the supramolecular framework of boron clusters, coupled with a variety of dyes to develop a series of metal-free agent compounds, and demonstrated that these nonmetallic compounds have excellent CDT activities through experiments. Subsequently, the best performing Methylene Blue/[closo-B12H12]2- (MB@B12H12) was used as an example. Through theoretical calculations, electron paramagnetic resonance spectroscopy, and 808 nm light irradiation, we confirmed that MB@B12H12 exhibited photothermal performance and CDT activity further. More importantly, we applied MB@B12H12 to melanoma cells and subcutaneous tumor, demonstrating its effective suppression of melanoma growth in vitro and in vivo through the synergistic effects of photothermal performance and CDT activity. This study emphasizes the generalizability of the coupling of dyes to [closo-B12H12]2- with important clinical translational potential for CDT reagents. Among them, MB@B12H12 may have a brighter future, paving the way for the rapid development of metal-free CDT reagents.

Lignin‐Metal Supramolecular Framework Strategy of Self‐Healing Carbon‐Coated CoRu Alloy Nanocatalyst for Efficient Overall Water Splitting

AbstractCommon precursors for carbon materials typically include petroleum‐based polymers or MOF materials. However, these materials often encounter challenges such as metal aggregation, high cost, and metals leaching. In this work, a novel of approach lignin‐metal supramolecular framework complex (MSF@Lignin) is introduced. These complexes are formed through oxidative ammonolysis of lignin (OAL) to synthesize a nitrogen‐doped carbon‐encapsulated CoRu nanocatalyst (CoRu@OALC) via in situ carbonization. CoRu@OALC exhibited exceptional performance in both HER (90 mV) and OER (200 mV) at the current density of 10 mA cm−2, with an overall water splitting voltage of 1.5 V and outstanding stability under high density. During the pyrolysis process, metal became encapsulated by lignin‐derived carbon, occurring within the temperature range of 600–700 °C. In the catalytic process, active sites are primarily located within the defects in lignin‐derived carbon, showcasing a unique “self‐healing” phenomenon within the carbon layer. Oxygen‐containing intermediates (*OH, *O, and *OOH) facilitated the reconstruction of defects on the carbon layer, while the hydrogen‐containing intermediates (*H) contributed to the reappearance of a defect‐rich structure.

Two-dimensional crystallization of precise side-chain giant molecules with constant building blocks ratio

This paper describes the two-dimensional (2D) crystallization of side-chain giant molecules (SCGMs) having the fixed number ratio of two types of functionalized building blocks with 1:1. SCGMs are regarded to a certain degree as size-amplified versions of universal synthetic polymers that are prepared by precisely connecting molecular nanoparticles (MNPs) to polymer chains. Our previous experimental results have shown that individually changing the number ratio of one of the building blocks would significantly affect the structural parameters of molecular crystals, mainly the longitudinal thickness. Herein, we systematically discussed the 2D crystallization of two categories of POSS-based SCGMs with constant building blocks ratio. Solution self-assembly of such SCGMs resulted in well-defined 2D nanosheets with similar structural configurations, showing great tolerance in the number of building blocks. Subsequently, we proposed a “sandwiched-type” mode to illustrate the bilayer 2D supramolecular framework, in which crystalline blocks pack in head-to-head manner. In addition, sequence isomers provide an ideal platform to further verify that the thickness of 2D nanocrystal is linked with the tethering density determined by the number ratio of building blocks. We believe that this study could be a better complement to our previous work and then make us to be more in-depth understand the crystallization mechanism of SCGMs.

Bis{(S)-(-)-N-[(2-biphen-yl)methyl-idene]-1-(4-meth-oxy-phen-yl)ethyl-amine-κN}di-chlorido-palladium(II).

The PdII complex bis-{(S)-(-)-N-[(biphenyl-2-yl)methyl-idene]1-(4-meth-oxy-phen-yl)ethanamine-κN}di-chlorido-palladium(II), [PdCl2(C22H21NO)2], crystallizes in the monoclinic Sohncke space group P21 with a single mol-ecule in the asymmetric unit. The coordination environment around the palladium is slightly distorted square planar. The N-Pd-Cl bond angles are 91.85 (19), 88.10 (17), 89.96 (18), and 90.0 (2)°, while the Pd-Cl and Pd-N bond lengths are 2.310 (2) and 2.315 (2) Å and 2.015 (2) and 2.022 (6) Å, respectively. The crystal structure features inter-molecular N-H⋯Cl and intramolecular C-H⋯Pd inter-actions, which lead to the formation of a supramolecular framework structure.

Organic cage-based frameworks: from synthesis to applications

The investigation of organic cage-based frameworks (OCFs) has attracted increasing attention over the past decade due to their versatile synthetic methods and broad property range resulting from the unique combination of porous organic cages (POCs) with diverse framework materials, including porous organic polymers (POPs), metal-organic frameworks (MOFs), and supramolecular organic frameworks (SOFs). Nevertheless, a comprehensive summary of the research advancements in OCFs remains elusive in the literature. This review addresses this gap by providing a detailed overview of the development of OCF-based materials from both synthetic and applicative perspectives. The discussion begins with systematically exploring design principles and common strategies for elaborating OCFs, achieved by rational selection of bond-forming routes suitable for various POC monomers, including covalent bonds, coordination bonds, and supramolecular interactions. Subsequently, the review highlights the functional attributes derived from the distinctive structural features of OCFs, showcasing their task-specific applications in adsorption/separation, catalysis, membrane technology, and other fields. Lastly, the article summarizes the opportunities and challenges anticipated as the exploration of the OCF family continues to advance in material science.

Structural diversity of transition-metal coordination polymers and dinuclear metallocycles constructed by bispyridyl-substituted diphthalic diimide ligands

Four coordination polymers (CPs), namely, {[Ni(L1)2Cl2]·(CHCl3)}n(1), {[Co(L1)1.5(NO3)2]·(CHCl3)}n (2), {[Ag2(L2)2(NO3)2]·(CHCl3)}n (3), [Cd(L2)2(Cl)2]n (4), and two dinuclear metallocycles, namely, {[Zn2(L3)2(Cl)4]·2CHCl3}n (5) and [Cu2(L3)2(Cl)4] (6), (L1 = 2,2′-bis(pyridin-3-ylmethyl)-[5,5′-biisoindoline]-1,1′,3,3′-tetraone), L2 = 5,5′-oxybis(2-(pyridin-3-ylmethyl)isoindoline-1,3-dione), L3 = 5,5′-carbonylbis(2-(pyridin-3-ylmethyl)isoindoline-1,3-dione)), have been adeptly constructed using solvothermal conditions and successfully delineated by non-destructive single-crystal (X-ray) diffraction. Structural analyses provide insights into a two-dimensional (2D) 44 grid layer of complex 1 and a three-dimensional (3D) 63 network of 2. Additionally, the connection between these two complexes is established via hydrogen bonding (CH···O) to further accomplish a three-dimensional (3D) supramolecular framework system. Similarly, Complex 3 and 4 possess a one-dimensional (1D) wave-like chain and loop-like chains composed of olive-like metallacycle building units, respectively. These chains are bridged by CH···O hydrogen bond and π∙∙∙π stacking interactions to generate 3D supramolecular structure. Finally, complexes 5 and 6 occupies zero-dimensional (0D) square-like array also called as olive-like dimeric M2L2 metallacycles. The distinct structural configurations of the six complexes are in close alliance with different conformations of the N-donor pyridyl ligands and coordination arrangement of the transition metal centers.

Electron transfer-mediated peroxymonosulfate activation through monoatomic Fe–pyridinic N4 moiety in biochar-based catalyst for electron-rich pollutants degradation in groundwater

Pollution of groundwater by electron-rich refractory organic pollutants (e-ROPs) is detrimental to ecological integrity and human health. Biochar (BC)-based single-atom Fe catalysts (Fe–SACs) triggering nonradical peroxymonosulfate (PMS) process has shown great potential in addressing this problem. Nevertheless, the successful formation and precise regulation of active sites on BC remain formidable challenges. Herein, co-pyrolysis of BC derived from shrimp shells and N-containing supramolecular organic frameworks with a hexagonal cavity structure of Fe3+–N3 (Fe–SOFs) was, for the first time, used to prepare an efficient and inexpensive BC-based Fe–SAC (Fe–MCA@SS). The Fe–N bond was successfully grafted from Fe–SOFs onto BC and subsequently transformed into monoatomic Fe–pyridinic N4. Moreover, Fe–MCA@SS successfully triggered an efficient nonradical PMS process, degrading 94.5 % of aniline (AN) within 5 min. Mediated electron transfer (MET) mechanism was primarily responsible for AN removal. MET was attributed to the following factors: the synergistic effect of the stronger chemical adsorption of PMS with an Fe atom in Fe–pyridinic N4 active sites, the higher redox potential of [Fe–MCA@SS/PMS]*, and the value of the lowest unoccupied molecular orbital of AN being larger than the value of highest occupied molecular orbital of [Fe–MCA@SS/PMS]*. This study sheds new light on the preparation of BC-based SACs catalyst with efficient nonradical oxidation ability and an excellent feasibility to remove electron-rich organic pollutants in groundwater.

An Organodiphosphate-Containing Polyoxoniobate Ring and Its Assembly into a Three-Dimensional Framework through Hydrogen Bonding.

In this work, a novel organodiphosphate-containing inorganic-organic hybrid polyoxoniobate (PONb) ring {(PO3CH2CH2PO3H)4Nb8O16}4- (Nb8P8) has been achieved by a one-pot hydrothermal method. The ring is constructed from a tetragonal {Nb8O36} motif and four {PO3CH2CH2PO3H} ligands. Interestingly, Nb8P8 can be joined together via K-H2O clusters {K2(H2O)4(OH)2} to form one-dimensional chains {[K2(H2O)4(OH)2]Nb8P8}n and further linked by {Cu(en)2}2+ (en = ethylenediamine) complexes, resulting in a three-dimensional supramolecular framework {[Cu(en)2]2[K2(H2O)4(OH)2]Nb8P8}·3en·H2O (1). 1 exhibits good chemical and thermal stability and has a high water vapor adsorption capacity of ≤224 cm3 g-1 (22.71 mol·mol-1) at 298 K, outperforming most of the known polyoxometalate-based materials. Impedance measurements prove that 1 can transfer protons with moderate conductivity. This study not only contributes to the structural diversity of organodiphosphate-containing PONbs and PONb rings but also provides a reference for the development of PONb-based materials with unique performance.

Supramolecular frameworks assembled by [EuL2]3+ units with different coordination configurations

Self-assembly is an important strategy to construct supramolecular frameworks. Small change in the assembling units often leads to significant variations in the self-assembly structures. In the work, we obtain two supramolecular frameworks assembled by different [EuL2]3+ units (L = tris((5,6-dimethyl-1H-benzo[d]imidazol-2-yl)methyl) amine). One meso compound {[EuⅢL2]·(H2O)6·Cl3} (Meso-EuL2) is assembled by an achiral meso-[EuL2]3+ unit, forming a supramolecular three-dimensional framework through six-fold intermolecular π‒π interactions. The other is a racemic compound {[EuⅢL2]·(CH3OH)5·Cl3} (Rac-EuL2), assembled by two chiral rac-[EuL2]3+ units predominantly via hydrogen bonding, leading to a layered supramolecular framework. The luminescent properties are different between Meso-EuL2 and Rac-EuL2, with Meso-EuL2 exhibiting more excimer-like emissions, which is likely caused by its stronger π‒π interactions in the structure.

Two robust zinc(II) complexes as multi-functional luminescence sensor for detection of Fe3+, Cr2O72−, and CrO42− ions in water

Two new zinc(II) complexes, namely, [Zn(BBOP)(TPA)0.5]n (1) and [Zn(BBOP)(NDC)·H2O]n (2) (H2TPA = terephthalic acid, H2NDC = 1,4-naphthalene dicarboxylic acid, BBOP = 1,3-bis(benzimidazol-2-yl)-2-oxapropane) are hydrothermally synthesized and characterized. 1 features a 3D 2-fold interpenetrated 3-connected SrSi2-type framework. 2 is a mononuclear Zn(II) complex and further extend into the 3D supramolecular framework by OH⋯O and NH⋯O hydrogen bonding interactions. 1 and 2 both manifest high chemical stability. Two luminescence complexes are excellent sensors for the luminescent detection of Fe3+, Cr2O72−, and CrO42− ions in an aqueous medium. The quenching mechanism of the complexes is also investigated.

Experimental and theoretical studies of trinuclear cadmium(II) complex containing pyridine ring: Synthesis, crystallographic, spectroscopic, TD/DFT calculations and Hirshfeld surface analysis

Two three-dimensional supramolecular structures of L and [Cd3L2(CH3OH)4Cl6] complex (L = 2-(6-bromopyridin-2-yl)-4-methyl-1,2-dihydroquinazoline-N3-oxide), were synthesized and characterized by X-ray crystallography and elemental analysis, as well as FT-IR, UV–Vis, and fluorescence spectroscopy. The photoluminescence behavior of the Cd(II) complex was also investigated in different solvents. X-ray diffraction analysis results revealed that the Cd(II) complex was a trinuclear hexa-coordinate structure and made up of two L, three Cd2+ metal central, four methanol and six chlorine ions. In the crystal structures, it was noteworthy that L formed an infinite 1-D chain-like, 2-D square structure, parallelogram 3-D supramolecular skeleton, whereas the Cd(II) complex formed an infinite 1-D chain-like, 2-D ladder-like configuration, and even expanding into 3-D grid-like supramolecular frameworks. Density functional theory (DFT) calculation was used to compute the optimization, molecular frontier orbital energies (HOMO and LUMO). Specifically, owing to the combination of metal orbitals and the ligand, the energy gap of the complex was less than L. Electrostatic potential (ESP) was used to analyze the reaction sites of two compounds. On the basis of optimized geometry, time-dependent DFT (TD-DFT) simulated the electronic transitions rationalized the UV–Vis spectra peaks of L and Cd(II) complex. In addition, some non-covalent interactions were quantified by Hirshfeld surface and analyzed by Interaction region indicator (IRI).

Self-Assembled Supramolecular Frameworks and Interaction Energy Studies of Acridine and Dihydroxynaphthalene Based Cocrystals

Self-Assembled Supramolecular Frameworks and Interaction Energy Studies of Acridine and Dihydroxynaphthalene Based Cocrystals

Supramolecular polynuclear clusters sustained cubic hydrogen bonded frameworks with octahedral cages for reversible photochromism

Developing supramolecular porous crystalline frameworks with tailor-made architectures from advanced secondary building units (SBUs) remains a pivotal challenge in reticular chemistry. Particularly for hydrogen-bonded organic frameworks (HOFs), construction of geometrical cavities through secondary units has been rarely achieved. Herein, a body-centered cubic HOF (TCA_NH4) with octahedral cages was constructed by a C3-symmetric building block and NH4+ node-assembled cluster (NH4)4(COOH)8(H2O)2 that served as supramolecular secondary building units (SSBUs), akin to the polynuclear SBUs in reticular chemistry. Specifically, the octahedral cages could encapsulate four homogenous haloforms including CHCl3, CHBr3, and CHI3 with truncated octahedron configuration. Crystallographic evidence revealed the cages served as spatially-confined nanoreactors, enabling fast, broadband photochromic effect associated with the reversible photo/thermal transformation between encapsulated CHI3 and I2. Overall, this work provides a strategy by shaping SSBUs to expand the framework topology of HOFs and a prototype of hydrogen-bonded nanoreactors to accommodate reversible photochromic reactions.

Exploring the synthesis, structure, and properties of two 2D transition metal polymers based on 4, 4’-bistriazole 3, 3’-biphenyldicarboxylic acid

Two coordination polymers {[Zn(BTBPA)(H2O)2]·0·5H2O}n (Zn-1), and {[Mn(BTBPA)(H2O)2]·0·5H2O}n (Mn-2) were synthesized solvothermally by the combination of organic linker 4,4′-bistriazole 3,3′-biphenyldicarboxylic acid (H2BTBPA) and Zn(NO3)2·6H2O or MnCl2·4H2O. Both of the polymers 1–2 are as 4,4-linked two-dimensional layered structures, which constitute into three dimensional supramolecular frameworks with porous channels via O − H⋅⋅⋅O hydrogen bonds. Zn-1 exhibits recognition abilities to antibiotics (PCL, NFT and NFZ) with high sensitivity via luminescence “turn-off” mechanism. In addition, the static magnetic performance of Mn-2 was investigated.

In Situ Grown Coordination-Supramolecular Layer Holding 3D Charged Channels for Highly Reversible Zn Anodes.

Dynamic reversible noncovalent interactions make supramolecular framework (SF) structures flexible and designable. A three-dimensional (3D) growth of such frameworks is beneficial to improve the structure stability while maintaining unique properties. Here, through the ionic interaction of the polyoxometalate cluster, coordination of zinc ions with cationic terpyridine, and hydrogen bonding of grafted carboxyl groups, the construction of a 3D SF at a well-crystallized state is realized. The framework can grow in situ on the Zn surface, further extending laterally into a full covering without defects. Relying on the dissolution and the postcoordination effects, the 3D SF layer is used as an artificial solid electrolyte interphase to improve the Zn-anode performance. The uniformly distributed clusters within nanosized pores create a negatively charged nanochannel, accelerating zinc ion transfer and homogenizing zinc deposition. The 3D SF/Zn symmetric cells demonstrate high stability for over 3000 h at a current density of 5 mA cm-2.

Synthesis, molecular self-assembly and anti-carcinogenic study of 2-pyridone molecules

4H-pyrans obtained from the multicomponent reactions of aromatic aldehyde, malononitrile, and ethyl acetoacetate were used as a starting scaffold for synthesizing 2-pyridone derivatives (1–3). Two catalytic methods were reported for the conversion of 4H-pyrans to 3,4-dihydropyridones. The non-aromatic 3,4-dihydropyridones obtained were then oxidized to give the final desired 2-pyridone derivatives (1–3). Crystals of the synthesized compounds were prepared and subjected to single-crystal X-ray crystallography (SCXRD) to acquire their structural parameters. Non-covalent interactions in the supramolecular systems 1–3 were studied, and it found that NH∙∙∙O interactions between the lactam groups are the most dominant hydrogen bonds. It is also observed that the aromatic rings are involved in lone pair∙∙∙π, CH∙∙∙π, and weak π∙∙∙π interactions in assisting the supramolecular framework. Hirshfeld surface studies are also performed to validate the interactions within the supramolecular crystals. The 2-pyridone derivatives (1–3) were also analyzed by in vitro techniques to evaluate their cytotoxic activities using human lung adenocarcinoma (A549). It is also found that ethyl 5-cyano-2-methyl-4-(3-nitrophenyl)-6-oxo-1,6-dihydropyridine-3-carboxylate (1) has shown the highest cytotoxic potency amongst the synthesized compound.

Visible light-mediated supramolecular framework for tunable CO2 adsorption

In the pursuit of creating azobenzene-functionalized photo-responsive supramolecular frameworks (PSMFs) activated by the visible spectrum, an endeavor traditionally relied on ultraviolet activation, we report the successful fabrication of a visible light-mediated metal–organic cage-based PSMF, designated as NUT-104. This achievement was realized by the hierarchical self-assembly process of Zr-metal–organic cages featuring ortho-fluoroazobenzene functional terephthalic acid and tri-nuclear Zr-clusters. NUT-104 displays permanent porosity coupled with reversible responsiveness to visible light. This remarkable behavior emerges as a consequence of the σ-electron-withdrawing effect induced by the presence of fluorine substituents. Visible light-regulated CO2 adsorption capacity can be achieved and the change value can reach 61 %, while the change for CH4 and N2 is only 7 % and 3 %, respectively. In response to irradiation at wavelengths of 520 and 420 nm, respectively, the azobenzene moieties within the NUT-104 structure exhibit a remarkable capacity for visible light-controlled reversible conformational changes. Grand Canonical Monte Carlo simulations unveiled that the dynamic reorganization of the NUT-104 proficiently governs the accessibility of CO2 adsorption sites positioned within the interstitial regions of proximate cages. The advent of NUT-104, underpinned by its visible light responsiveness and versatile tunability, paves the way for avenues of exploration in controlled gas separation and storage applications.