Three-dimensional Metal-organic Framework Research Articles

From two-dimensional networks to three-dimensional metal–organic frameworks mediated by solvent ratio: luminescence and gas adsorption properties

Various two-dimensional networks ((4,4) network and unique quasi-“long and short brick” network) and three-dimensional frameworks are induced only through changing the solvent ratio (acetonitrile : water).

From zero-dimensional metallomacrocycle to three-dimensional metal–organic frameworks mediated by solvent polarity: near-white light emissions and gas adsorption properties

The changes from 0D metallomacrocycle to 3D frameworks are mediated by solvent polarity: single-component near-white light emissions.

A one-dimensional conductive metal-organic framework with extended π-d conjugated nanoribbon layers

Conductive metal-organic frameworks (MOFs) have performed well in the fields of energy and catalysis, among which two-dimensional (2D) and three-dimensional (3D) MOFs are well-known. Here, we have synthesized a one-dimensional (1D) conductive metal-organic framework (MOF) in which hexacoordinated 1,5-Diamino-4,8-dihydroxy-9,10-anthraceneedione (DDA) ligands are connected by double Cu ions, resulting in nanoribbon layers with 1D π-d conjugated nanoribbon plane and out-of-plane π-π stacking, which facilitates charge transport along two dimensions. The DDA-Cu as a highly conductive n-type MOF has high crystalline quality with a conductivity of ~ 9.4 S·m−1, which is at least two orders of magnitude higher than that of conventional 1D MOFs. Its electrical band gap (Eg) and exciton binding energy (Eb) are approximately 0.49 eV and 0.3 eV, respectively. When utilized as electrode material in a supercapacitor, the DDA-Cu exhibits good charge storage capacity and cycle stability. Meanwhile, as thse active semiconductor layer, it successfully simulates the artificial visual perception system with excellent bending resistance and air stability as a MOF-based flexible optoelectronic synaptic case. The controllable preparation of high-quality 1D DDA-Cu MOF may enable new architectural designs and various applications in the future.

Vacuum-Induced Guest N,N'-Diethylformamide Binding in a Metastable Cd5-Based Metal-Organic Framework.

A three-dimensional (3D) metal-organic framework (MOF) of [Et2NH2]2[Cd5(BTB)4(DEF)2]·4.75DEF (1; H3BTB = benzene-1,3,5-tribenzoic acid and DEF = N,N'-diethylformamide) sustained by symmetrical Z-shaped Cd5 secondary building units (SBUs) with an intrinsically metastable host framework has been prepared and characterized. Upon gentle vacuum (800 Pa) at 50 °C, some encapsulated DEF solvates are released, leading to pore-shape changes and Cd2+ coordination geometry distortion. This is followed by DEF solvate migration to only one end of the SBU with concomitant symmetry breaking. Additional time under vacuum promoted further structural distortion and topology changes as authenticated by single-crystal X-ray diffraction studies. This work was initially inspired by unusual gas adsorption isotherms and points to the potentially complicated, nonspectator role of coordinative solvents such as DEF during MOF activation.

Highly Luminescent Crystalline Sponge: Sensing Properties and Direct X-ray Visualization of the Substrates.

A phenomenon of crystalline sponge is represented by guest-dependent structural fluidity of the host polymeric lattice in highly crystalline sorbents, such as metal-organic frameworks, driven by multiple weak intermolecular interactions. Such induced fitting in MOFs is a valuable property in selective adsorption, guest determination by single-crystal XRD and in-situ structural analysis under external stimuli. In this work, a porous three-dimensional metal-organic framework [Eu2(DMF)4(ttdc)3]·4.45DMF (1DMF; DMF = N,N-dimethylformamide, ttdc2- = trans-thienothiophenedicarboxylate anion) was applied as a crystalline sponge bearing luminescent functionality to couple its sensing properties with direct structural determination of the adsorbed molecules. As a result, the paper discusses crystal structures and luminescent properties for the successfully obtained new adducts with the crystallographic formulae [Eu2(DMSO)4(ttdc)3]·2.5DMSO·2.2H2O (1DMSO; DMSO = dimethylsulfoxide), [Eu2(DMF)4(ttdc)3]·3phet (1phet; phet = phenylethanal) and [Eu2(DMF)3.5(cin)0.5(ttdc)3]·1.64cin (1cin; cin = trans-cinnamaldehyde). As a result of inclusion of DMSO into 1, a slight increase in the quantum yield and excited state phosphorescence lifetime was observed, while the adsorption of phet leads to a considerable (up to three times) decrease in the corresponding values. The incorporation of cinnamal results in a full quenching of QY, from 20% down to zero, and a more than order of magnitude diminishing of the excited state lifetime compared to the initial 1DMF. The effective sensing of cinnamal was explained from the structural point of view by its direct coordination to the Eu3+ emitter, as well as by multiple weak intermolecular interactions with ttdc antenna ligand, both capable of enhancing the non-radiative energy dissipation.

Potential of a pH-Stable Microporous MOF for C2H2/C2H4 and C2H2/CO2 Gas Separations under Ambient Conditions.

Cost-effective adsorption-based C2H2/C2H4 and C2H2/CO2 gas separations are extremely important in the industry. Herein, a pH-stable three-dimensional (3D) metal-organic framework (MOF), IITKGP-25, possessing exposed functional sites is presented, which facilitates such separations with excellent ideal adsorbed solution theory (IAST) selectivity (4.61 for C2H2/C2H4 and 3.93 for C2H2/CO2) under ambient conditions (295 K, 100 kPa, 50:50 gas mixtures) and a moderate affinity toward C2H2 (26.6 kJ mol-1). Interestingly, IITKGP-25 can maintain structural integrity in water and in aqueous acidic/alkaline (pH = 2-10) medium because of the higher coordination numbers around the metal center and the hydrophobicity of the ligand. The adsorption capacity for C2H2 remains unchanged for a minimum of up to five consecutive cycles and 15 days of exposure to 97% relative humidity, which are the prerequisites of an adsorbent for practical gas separation application. Density functional theory (DFT) calculations reveal that the open Cd(II) sites and carboxylate oxygen-coordinated Cd(II) corner of the triangle-shaped one-dimensional (1D) channel are the enthalpically more preferred binding sites for C2H2, which stabilize the adsorbed C2H2 through nonlocal stronger H-bonding and also pπ-dπ and CH-π interactions.

Coordination Polymers Constructed from an Adaptable Pyridine-Dicarboxylic Acid Linker: Assembly, Diversity of Structures, and Catalysis.

4,4'-(Pyridine-3,5-diyl)dibenzoic acid (H2pdba) was explored as an adaptable linker for assembling a diversity of new manganese(II), cobalt(II/III), nickel(II), and copper(II) coordination polymers (CPs): [Mn(μ4-pdba)(H2O)]n (1), {[M(μ3-pdba)(phen)]·2H2O}n (M = Co (2), Ni (3)), {[Cu2(μ3-pdba)2(bipy)]·2H2O}n (4), {[Co(μ3-pdba)(bipy)]·2H2O}n (5), [Co2(μ3-pdba)(μ-Hbiim)2(Hbiim)]n (6), and [M(μ4-pdba)(py)]n (M = Co (7), Ni (8)). The CPs were hydrothermally synthesized using metal(II) chloride precursors, H2pdba, and different coligands functioning as crystallization mediators (phen: 1,10-phenanthroline; bipy: 2,2'-bipyridine, H2biim: 2,2'-biimidazole; py: pyridine). Structural networks of 1-8 range from two-dimensional (2D) metal-organic layers (1-3, 5-8) to three-dimensional (3D) metal-organic framework (MOF) (4) and disclose several types of topologies: sql (in 1), hcb (in 2, 3, 5), tfk (in 4), 3,5L66 (in 6), and SP 2-periodic net (6,3)Ia (in 7, 8). Apart from the characterization by standard methods, catalytic potential of the obtained CPs was also screened in the Knoevenagel condensation of benzaldehyde with propanedinitrile to give 2-benzylidenemalononitrile (model reaction). Several reaction parameters were optimized, and the substrate scope was explored, revealing the best catalytic performance for a 3D MOF 4. This catalyst is recyclable and can lead to substituted dinitrile products in up to 99% product yields. The present study widens the use of H2pdba as a still poorly studied linker toward designing novel functional coordination polymers.

Structural Diversity and Carbon Dioxide Sorption Selectivity of Zinc(II) Metal-Organic Frameworks Based on Bis(1,2,4-triazol-1-yl)methane and Terephthalic Acid

A three-component reaction between the 1,4-benzenedicarboxylic (terephthalic) acid (H2bdc), bis(1,2,4-triazol-1-yl)methane (btrm) and zinc nitrate was studied, and three new coordination polymers were isolated by a careful selection of the reaction conditions. Coordination polymers {[Zn3(DMF)(btrm)(bdc)3]·nDMF}∞ and {[Zn3(btrm)(bdc)3]·nDMF}∞ containing trinuclear {Zn3(bdc)3} secondary building units are joined by btrm auxiliary linkers into three-dimensional metal–organic frameworks. The coordination polymer {[Zn(bdc)(btrm)]∙nDMF}∞ consists of Zn2+ cations joined by bdc2− and btrm linkers into a two-fold interpenetrated network. Upon activation, MOF [Zn3(btrm)(bdc)3]∞ demonstrated CO2/N2 adsorption selectivity with an ideal adsorbed solution theory (IAST) factor of 21. All three MOF demonstrated photoluminescence with a maximum near 435–440 nm upon excitation at 330 nm.

Aliphatic-Bridged Early Lanthanide Metal–Organic Frameworks: Topological Polymorphism and Excitation-Dependent Luminescence

Six new three-dimensional metal–organic frameworks based on early lanthanide(III) cations and trans-1,4-cyclohexanedicarboxylic acid (H2chdc) were obtained. Their crystal structures were determined by single-crystal X-ray diffraction analysis. The structure of [La2(H2O)4(chdc)3]·2DMF·H2O (1; DMF = N,N-dimethylformamide) contains one-dimensional infinite La(III)-carboxylate chains interconnected by cyclohexane moieties to form a highly porous polymeric lattice with 30% solvent accessible volume. Compounds [Ln2(phen)2(chdc)3]·0.75DMF (2Ln; Ln3+ = Ce3+, Pr3+, Nd3+ and Sm3+; phen = 1,10-phenanthroline) are based on binuclear carboxylate building blocks, which are decorated by chelate phenanthroline ligands and interconnected by cyclohexane moieties to form more dense isostructural coordination frameworks with primitive cubic pcu topology. Compound [Nd2(phen)2(chdc)3]·2DMF·0.67H2O (3) is based on secondary building units similar to 2Ln and contains a coordination lattice isomeric to 2Ln with a rare hexagonal helical snz topology. Thermal stability and luminescent properties were investigated. For 2Sm, a strong and nonmonotonous dependence of the luminescence color on the variation of excitation wavelength was revealed, changing its emission from pinkish red at λex = 340 nm to white at λex = 400 nm, and then to yellow at lower excitation energies. Such nonlinear behavior was rationalized in terms of the contribution of several different luminescence mechanisms. Thus, 2Sm is a rather rare example of a highly tunable monometallic lanthanide-based luminophore with possible applications in light-emitting devices and optical data processing.

A computational study of metal–organic frameworks (MOFs) as potential nanostructures to combat SARS-CoV-2

The COVID-19 causative agent, severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), has a critical surface protein called spike protein (S protein), which is the target of many vaccines and drugs developments. Among non-structural proteins of SARS-CoV-2, main protease (Mpro) has drawn much attention to itself for designing antiviral drugs since it is very crucial for the virus replication in host cells. In the first part of the present study, the application of metal–organic frameworks (MOFs), one of the developing nanomaterials in the deformation and consequently inhibition of S protein binding to the receptor, angiotensin-converting enzyme 2 (ACE 2), is investigated. In this line, various S protein inhibitors were designed virtually, including ZIF, UIO, and IRMOF that their interactions with S protein and were investigated using molecular dynamics (MD) simulation. The results revealed that ZIF is the best candidate among the investigated MOFs with the least amount of energy interference with S protein. In the second part, the interaction of three-dimensional (3D) MOFs (such as ZIF, IRMOF, and HKUST) with SARS-CoV-2 Mpro was investigated. HKUST had the most potent interaction with Mpro and showed more promise in deforming this protein's secondary structure among all materials tested. Furthermore, we investigated the interaction of HKUST-OH with Mpro to determine the effect of functionalization. The findings of this study could be used in future studies to introduce bioconjugates of MOFs and biological molecules (e.g., antibody or nanobody) or to use MOFs as carriers for antiviral drug delivery.

Exploring a metalloligand for construction of an oxamato-based metal-organic framework

We report the two-step synthesis of a heterobimetallic oxamato-based metal-organic framework (MOF). First, we prepared an oxamato functionalized carbazole-based dinuclear copper(II) complex, K4{Cu2(carbox)2]}·8H2O, where the carbozale linkers exhibited an uncommon substitution pattern, carbox = N,N’-1,6-carbazolebis(oxamate). Then, this building block was used as a metalloligand toward manganese(II) metal ions to assemble a neutral three-dimensional (3 D) MOF with formula [Mn2Cu2(carbox)2(H2O)4]·6CH3OH·2H2O (1) and single-crystal X-ray diffraction determined the structure. The resulting network constitutes one of the few examples of oxamato-based 3 D MOF.

Nitrogen-rich three-dimensional metal-organic framework microrods as an efficient electrocatalyst for oxygen evolution reaction and supercapacitor applications

The development of a smart and simple “one stone two birds” synthetic strategy to design remarkable electrode material for green energy harvesting and storage has always been challenging. Among the materials, metal–organic frameworks (MOFs)are the most potential hotspot for developing state-of-the-art materials for efficient oxygen evolution and energy storage application because of their fascinating chemical and structural traits. Herein we present a wet chemical method for the synthesis of a binder-free electrocatalyst for oxygen evolution and an admirable supercapacitor electrode. The designed 3D MOF (AgTz-1) exhibits excellent electrocatalytic oxygen evolution activity, with an ultralow overpotential (η) of 196 mV at 10 mA cm−2 and a Tafel slope of 114 mV dec-1. Furthermore, the AgTz-1-based electrode has a high energy density of 49.5 Wh kg−1 at a power density of 545 W kg−1. The results demonstrated not only a benchmark for pristine MOF in electrocatalysis and energy storage but also a novel family of nitrogen-rich MOF to enhance electrocatalytic performance due to significant active sites.

Infusion of Variable Chemical Structure to Tune Stacking among Metal-Organic Layers in 2D Nano MOF.

Thickness of two-dimensional (2D) metal-organic frameworks (MOFs) govern their intriguing functionalities. Primarily this thickness is controlled by the stacking between the metal-organic layers (MOL). It is observed that until now such modulating factors for stacking efficiency of MOL are not well studied. Here, we report a fundamental hypothesis to comprehend regulation of stacking efficiency among MOLs as a function of chemical structure of organic ligands (dicarboxylic acids and pillar linkers). This basically involves a series of isostructural three-dimensional (3D) MOFs which contain linkers of variable chemical nature that could be depillared to generate 2D stacked MOFs of different thickness. Depending on the linkers, we encountered the formation of single MOL to stacked multiple MOLs as evidenced from atomic force microscopic and other experimental analysis. The present study gives a concrete correlation between the stacking within 2D MOFs (from monolayer to multilayers), and their 3D counter parts, which may provide a thickness tuning pathway for 2D MOFs.

Synergistic Multiple Bonds Induced Dynamic Self-Assembly of Silver Nanoclusters into Lamellar Frameworks with Tailored Luminescence

Incorporating atomically precise metal nanoclusters (NCs) into ordered self-assemblies endows them with advanced photophysical properties; however, their ordered arrangement in space is difficult to achieve with only noncovalent bonds between individual clusters. Herein, we illustrate the hierarchical self-assembly of atomically precise silver NCs (NH4)6[Ag6(mna)6] (Ag6-NCs) into hexagonal two-dimensional lamellas by intercluster π···π and C-H···π interactions, which then pack into three-dimensional metal–organic frameworks (MOFs) by the metal–ligand coordination interaction. Synergistic multiple bond-induced dynamic coassembly greatly enhanced the quantum yields and lifetimes, achieving the transformation of weak fluorescence to strong thermally activated delayed fluorescence (TADF). The structure and luminescence transformation could be reversibly switched by tuning the pH values. The Ag6-NCs/Ca2+ coassemblies behaved as efficient yellow phosphors to afford white light emitting diode devices. This work demonstrates a synergistic multiple bond-induced hierarchical self-assembly to realize ordered layer-by-layer MOFs from NCs-based secondary building units with advanced TADF emission in a pH-tailored manner for potential applications in luminescent devices and sensors.

High-throughput screening of metal–organic frameworks for hydrogen purification

In industry, the separation/purification of hydrogen from methane impurity is of significant importance, especially under the background of carbon dioxide mitigation towards carbon neutrality. Adsorption separation is an effective route for this application regarding energy cost and separation efficiency, for which the selection of adsorbents is the key. This work proposes a computer-aided high-throughput screening strategy for the selection of metal–organic frameworks (MOFs) for CH4/H2 separation, striving to accelerate the practice of discovering better adsorbents for this particular application. Firstly, a prescreening was conducted on 12,020 computation-ready three-dimensional MOFs based on intuitive structure and chemical analysis, shortlisting 5,096 candidates. Secondly, a molecular simulation-assisted structure–property relationship analysis was performed based on small sampled MOFs, from which two structure criteria were derived for high-performing MOFs. Based on the criteria, a screening procedure was then carried out, narrowing the candidate MOFs down to 2,408. The rigorous molecular simulation was again applied to assess the separation performance metrics of these MOFs, covering adsorption selectivity, working capacity, adsorbent performance score, regenerability and separation potential. By analysing the simulated performance indicators, top-performing MOFs were identified and a more detailed analysis of the structure-performance relationship was carried out. Additionally, the impact of several practical factors, covering humidity, operation temperature and inlet gas composition, on the performance of the selected adsorbents in practice was explored. It was observed that the robustness of MOFs at humidity depends on their hydrophilicity and preferential adsorption sites. Meanwhile, operation temperature can be manipulated to accommodate flexible production scenarios.

Coordination Polymers from Biphenyl-Dicarboxylate Linkers: Synthesis, Structural Diversity, Interpenetration, and Catalytic Properties.

The present work explores two biphenyl-dicarboxylate linkers, 3,3'-dihydroxy-(1,1'-biphenyl)-4,4'-dicarboxylic (H4L1) and 4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylic (H4L2) acids, in hydrothermal generation of nine new compounds formulated as [Co2(μ2-H2L1)2(phen)2(H2O)4] (1), [Mn2(μ4-H2L1)2(phen)2]n·4nH2O (2), [Zn(μ2-H2L1)(2,2'-bipy)(H2O)]n (3), [Cd(μ2-H2L1) (2,2'-bipy)(H2O)]n (4), [Mn2(μ2-H2L1)(μ4-H2L1)(μ2-4,4'-bipy)2]n·4nH2O (5), [Zn(μ2-H2L1)(μ2-4,4'-bipy)]n (6), [Zn(μ2-H2L2)(phen)]n (7), [Cd(μ3-H2L2)(phen)]n (8), and [Cu(μ2-H2L2) (μ2-4,4'-bipy)(H2O)]n (9). These coordination polymers (CPs) were generated by reacting a metal(II) chloride, a H4L1 or H4L2 linker, and a crystallization mediator such as 2,2'-bipy (2,2'-bipyridine), 4,4'-bipy (4,4'-bipyridine), or phen (1,10-phenanthroline). The structural types of 1-9 range from molecular dimers (1) to one-dimensional (3, 4, 7) and two-dimensional (8, 9) CPs as well as three-dimensional metal-organic frameworks (2, 5, 6). Their structural, topological, and interpenetration features were underlined, including an identification of unique two- and fivefold 3D + 3D interpenetrated nets in 5 and 6. Phase purity, thermal and luminescence behavior, as well as catalytic activity of the synthesized products were investigated. Particularly, a Zn(II)-based CP 3 acts as an effective and recyclable heterogeneous catalyst for Henry reaction between a model substrate (4-nitrobenzaldehyde) and nitroethane to give β-nitro alcohol products. For this reaction, various parameters were optimized, followed by the investigation of the substrate scope. By reporting nine new compounds and their structural traits and functional properties, the present work further outspreads a family of CPs constructed from the biphenyl-dicarboxylate H4L1 and H4L2 linkers.

Three-dimensional flower-like Co-based metal organic frameworks as efficient multifunctional catalysts towards oxygen reduction, oxygen evolution and hydrogen evolution reactions

Design and development of cost-efficient multifunctional three-dimensional (3D) metal organic frameworks (MOFs) towards oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are very significant for green energy devices. Herein, a scalable one-pot solvothermal method is developed to obtain a series of multifunctional 3D flower-like MOFs. In addition, systematic studies are also conducted on the effects of various metal cations and N-containing ligands on the structures, compositions, and multifunctional performance of the obtained MOFs. As a result, 3D flower-like Co-MOFs using Co2+ as a metal cation and 2,2’:6′,2″-terpyridine as a N-containing ligand exhibit the highest multifunctional performance towards ORR, OER and HER. The scalable method provides a new prospect to design and develop other MOFs-based multifunctional catalysts.

Selective and Multicyclic CO2 Adsorption with Visible Light-Driven Photodegradation of Organic Dyes in a Robust Metal-Organic Framework Embracing Heteroatom-Affixed Pores.

Pore environment modulation with polarizing groups is one of the essential prerequisites for selective carbon dioxide (CO2) adsorption in metal-organic frameworks (MOFs), wherein judicious installation of the photocatalytic feature can promise visible light-triggered degradation of toxic organic dye molecules. However, astute amalgamation of both these attributes over a single MOF is rather rare, yet much anticipated in view of sustainable applications. Pore engineering is effectively harnessed in a Zn(II)-based three-dimensional (3D) MOF, CSMCRI-16 (CSMCRI = Central Salt and Marine Chemicals Research Institute), through mixed-ligand assembly of a N-rich linker (L), 4,4'-oxybis(benzoic acid) (H2oba) ligand, and [Zn2(CO2)4N2] paddle-wheel secondary building units (SBUs). The noninterpenetrated structure contains unbound nitrogen and accessible oxygen atom-decorated porous channels and exhibits admirable stability in diverse organic solvents, open air, and at elevated temperatures. The heteroatom-decorated porous channels facilitated excellent CO2 uptake in the activated MOF (16a) with high selectivity over N2 (CO2/N2: 155.3) at 273 K. The framework further exhibits reasonable CO2 affinity and multicyclic CO2 sorption recurrence without a significant loss in the uptake capacity. Benefitting from the presence of the [Zn2(CO2)4N2] cluster in conjugation with π-conjugated organic ligands, the extended 3D network revealed an optical band gap energy of 2.55 eV, which makes the MOF an efficient photocatalyst toward the degradation of the cationic dyes crystal violet (CV) and methylene blue (MB) in the presence of a simple 40 W visible light lamp without any assistance of external oxidants. The catalyst exhibits multicyclic performance and short reaction time in addition to the fact that catalytic efficiencies (CV: 97.2%, MB: 97.8%) are comparable to those of contemporary materials.

Self-assembled three-dimensional coordination polymer with ligand-unsupported Ag–Ag bonds based on tetrazole-1-acetic ligand: Synthesis, structure, and properties

A new compound, [Ag2(tza)(NO3)]n(1), was obtained by reactions of 1H-Tetrazole-1-acetic (Htza) with AgNO3, and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction, respectively. The X-ray diffraction analysis reveals that compound 1 is three-dimensional (3D) metal-organic framework constructed by double-layer architecture and the ligand-unsupported Ag–Ag bonds, and displays an unprecedented (3, 6)-connected topological network with 1D hexagon channels of two sizes. The 1D zigzag Ag-metallic chain built from ligand-supported Ag–Ag bonds is observed in 1. Furthermore, the photoluminescence of 1 has also been investigated, and the result exhibits blue photoluminescence in the solid state at room temperature, which shows that this complex may be a good candidate for photoactive material. According to the crystal structures, the TDDFT/6-31G(d) approach was applied to study the photoluminescence emission of 1, and the calculated results are in good agreement with the experimental results.

Topologically Driven Pore/Surface Engineering in a Recyclable Microporous Metal-Organic Vessel Decorated with Hydrogen-Bond Acceptors for Solvent-Free Heterogeneous Catalysis.

The use of metal-organic frameworks (MOFs) comprising custom-designed linkers/ligands as efficient and recyclable heterogeneous catalysts is on the rise. However, the topologically driven bifunctional porous MOFs for showcasing a synergistic effect of two distinct activation pathways of substrates (e.g., involving hydrogen bonding and a Lewis acid) in multicomponent organic transformations are very challenging. In particular, the novelty of such studies lies in the proper pore and/or surface engineering in MOFs for bringing the substrates in close proximity to understand the mechanistic aspects at the molecular level. This work represents the topological design, solid-state structural characterization, and catalytic behavior of an oxadiazole tetracarboxylate-based microporous three-dimensional (3D) metal-organic framework (MOF), {[Zn2(oxdia)(4,4'-bpy)2]·8.5H2O}n (1), where the tetrapodal (4-connected) 5,5'-(1,3,4-oxadiazole-2,5-diyl)diisophthalate (oxdia4-), the tetrahedral metal vertex (Zn(II)), and a 2-connected pillar linker 4,4'-bipyridine (4,4'-bpy) are unique in their roles for the formation, stability, and function. As a proof of concept, the efficient utilization of both the oxadiazole moiety with an ability to provide H-bond acceptors and the coordinatively unsaturated Zn(II) centers in 1 is demonstrated for the catalytic process of the one-pot multicomponent Biginelli reaction under mild conditions and without a solvent. The key steps of substrate binding with the oxadiazole moiety are ascertained by a fluorescence experiment, demonstrating a decrease or increase in the emission intensity upon interaction with the substrates. Furthermore, the inherent polarizability of the oxadiazole moiety is exploited for CO2 capture and its size-selective chemical fixation to cyclic carbonates at room temperature and under solvent-free conditions. For both catalytic processes, the chemical stability, structural integrity, heterogeneity, versatility in terms of substrate scope, and mechanistic insights are discussed. Interestingly, the first catalytic process occurs on the surface, while the second reaction occurs inside the pore. This study opens new ways to catalyze different organic transformation reactions by utilizing this docking strategy to bring the multiple components close together by a microporous MOF.