Lanthanide Metal-organic Frameworks Research Articles

High‐Loading L‐Arginine Stabilized in an Oxygen‐Rich Lanthanide Metal–Organic Framework Capable of NO Release and Self‐Quantifying Luminescence Detection

AbstractExogenous supplementation of L‐arginine (L‐Arg) facilitates the release of nitric oxide (NO) for gas therapy applications in tumor microenvironments rich in H2O2. However, direct administration inevitably leads to the premature release of hydrophilic L‐Arg in the bloodstream, potentially resulting in unstable plasma L‐Arg concentrations and subsequent adverse reactions. Therefore, it is crucial to identify efficient and stable high‐dose L‐Arg delivery carriers, albeit challenging. Here, the study has achieved high (≈94 mg g−1) and stable L‐Arg loading within a 12‐coordinated Yb‐based lanthanide metal‐organic framework (named Yb‐DOBDC, where DOBDC is 2,5‐dihydroxyterephthalic acid). Yb‐DOBDC features size‐matched apertures and oxygen‐rich pore microenvironments, securely entrapping L‐Arg through electrostatic interactions and conjugation effects, thereby enhancing the biostability of the drug during delivery. In vitro experiments demonstrate that L‐Arg‐loaded Yb‐DOBDC (L‐Arg@Yb‐DOBDC) promotes NO release upon H2O2 stimulation, and the Yb‐DOBDC framework exhibits good biocompatibility within cells. More interestingly, the near‐infrared‐luminescence‐emitting Yb‐DOBDC exhibits a “turn‐off” behavior upon gradual loading of L‐Arg, enabling self‐quantifying luminescence detection during the encapsulation process. Consequently, the L‐Arg@Yb‐DOBDC system designed in this work, with its high/stable loading capacity and self‐quantifying luminescence detection capability, holds theoretical research value and potential practical application prospects.

Dual Stimulus Responsive GO-Modified Tb-MOF toward a Smart Coating for Corrosion Detection.

Smart-sensing coatings that exhibit multistimulus response, rapid indication, and reusability are in urgent need to effectively enhance the practicability of coatings while accurately detecting metal corrosion. In this work, a reusable corrosion self-reporting coating with multiple pH and Fe3+ stimulus responses was first constructed by the integration of a composite fluorescent probe into the resin matrix. This composite sensor was constructed by combining a lanthanide metal-organic framework (Ln-MOF) based on terbium and trimeric acid (H3BTC) with graphene oxide (GO) nanosheets (GO@Tb-BTC). The incorporation of GO formed a sea-urchin-like structure, thereby increasing the specific surface area and active sites of the probe. The coatings were characterized by using electrochemical impedance spectroscopy (EIS), visual observation, and fluorescence spectrophotometry. The surface morphology, wettability, and adhesion of the coating samples were analyzed using SEM, XPS, hydrostatic contact angle test, and an adhesion test. EIS measurements in 3.5 wt % NaCl solution for 72 h demonstrated the superior corrosion protection performance of the 0.3 wt %/GO@Tb-BTC/WEP coating compared to blank coating, with the charge-transfer resistance reaching 4.33 × 107 Ω·cm2, which was 9.5 times higher than that of the pure coating. The bright green fluorescence of GO@Tb-BTC/WEP coating exhibited a turn-off response when there was an excess of OH-/H+, but it demonstrated a reversible turn-on fluorescence when the ambient pH returned to neutral. Furthermore, such Fe3+-triggered fluorescence quenching responded to concentrations as low as 1 × 10-6 M. The fluorescence quenching rate of both intact and damaged coatings surpassed that of visual and EIS detection methods. Significantly, the fluorescence in scratches was effectively quenched within 25 min using 0.3 wt %/GO@Tb-BTC/WPU coating for visual observation. GO@Tb-BTC demonstrated exceptional corrosion self-reporting capabilities in both epoxy and polyurethane systems, making it a versatile option beyond single-coating applications.

A multifunctional fluorescent Eu‐MOF probe: Its synthesis, structure, and sensing properties

Based on 3‐(2,4‐dicarboxylphenyl)‐6‐carboxylpyridine ligand (H3dpcp), a lanthanide metal–organic framework with the porous three‐dimensional structure was successfully synthesized, namely, [Eu (dpcp)(H2O)]n (1). The experimental results indicated that complex 1 exhibited stable luminescence in the range of pH = 2–11 in aqueous solution. It is noteworthy that complex 1 could recognize tryptophan (Trp) and trans, trans‐muconic acid (tt‐MA) molecules through the fluorescence quenching effect, and showed high sensitivity, selectivity, recoverability, anti‐interference, and low detection limits for the identification of Trp and tt‐MA in aqueous solution. In addition, the fluorescence mechanisms of complex 1 for sensing of tt‐MA and Trp were elucidated in detail.

Electrodeposition fabrication of WO3/EuMOF film for fluorescence switch

In recent years, lanthanide metal organic frameworks have been widely used in various fields because of their excellent fluorescence properties. Fluorescence switch has also been considered as a research hot spot and widely applied in many fields. The combination of fluorescent material and electrochromic material has emerged in the preparation of fluorescence switch. Herein, a simple and rapid electrodeposition method is proposed for the preparation of amorphous EuMOF film. The whole process takes only half an hour under room temperature. The prepared amorphous EuMOF film exhibits significant emission peaks characteristic of Eu3+ when excited by 277 nm UV lamp. In addition, the prepared EuMOF is also applied in an electrochromic device to construct WO3/EuMOF fluorescence switch by stepwise electrodeposition using polystyrene microsphere as template. By changing the voltage, the coloring and fading of the device color, and the quenching and recovery of fluorescence can be reversibly regulated, in order to achieve the control of the “on” and “off” states of the fluorescence switch.

Dual-ligand lanthanide metal-organic framework based ratiometric fluorescent platform for visual monitoring of aminoglycoside residues in food samples

Herein, a dual-emission Eu metal-organic framework (Eu-MOF) is prepared and used as the ratiometric fluorescence probe for ultrasensitive detection of aminoglycoside antibiotics (AGs). Due to the strong hydrogen bond interactions between AGs and Eu-MOF, the blue emission is enhanced while the red emission has little fluctuation in Eu-MOF with the addition of AGs, thus a good linear relationship with the logarithm of AGs concentrations from 0.001 to 100 μg/mL can be established for quantitative analysis. Good sensitivity with the detection limit of 0.33 ng/mL for apramycin, 0.32 ng/mL for amikacin and 0.30 ng/mL for kanamycin is achieved. The proposed assay demonstrates good selectivity and applicability for determination of AGs in real milk and honey samples. The Eu-MOF materials are further fabricated as fluorescent test papers for facile visual detection. The as-established ratio fluorescence platform offers a portable and economical way for rapid monitoring AGs residues in complex food samples.

A fluorescent terbium-metal-organic framework material for high-sensitivity detection of vomitoxin and oxytetracycline hydrochloride in water.

A unique luminescent lanthanide metal-organic framework (LnMOF)-based fluorescence detection platform was utilized to achieve sensitive detection of vomitoxin (VT) and oxytetracycline hydrochloride (OTC-HCL) without the use of antibodies or biomolecular modifications. The sensor had a fluorescence quenching constant of 9.74 × 106 M-1 and a low detection limit of 0.68 nM for vomitoxin. Notably, this is the first example of a Tb-MOF sensor for fluorescence detection of vomitoxin. We further investigated its response to two mycotoxins, aflatoxin B1 and ochratoxin A, and found that their Stern-Volmer fluorescence quenching constants were lower than those of VT. In addition, the fluorescence sensor realized sensitive detection of OTC-HCL with a detection limit of 0.039 μM. In conclusion, the method has great potential as a sensitive and simple technique to detect VT and OTC-HCL in water.

Dual-ligand Eu-MOF/CuS@Au Heterostructure Array-based ECL Sensor for MiRNA-128 Detection in Glioblastoma Tissues

In this work, the dual-ligand lanthanide metal-organic framework (MOF)-based electrochemiluminescence (ECL) sensor was constructed for the detection of miRNA-128 in glioblastoma (GBM) diagnosis. The luminescent Eu-MOF (EuBBN) was synthesized with terephthalic acid (BDC) and 2-amino terephthalic acid (BDC-NH2) as dual-ligand. Due to the antenna effect, EuBBN with conjugated-π structure exhibited strong luminescent signal and high quantum efficiency, which can be employed as ECL nanoprobe. Furthermore, the novel plasmonic CuS@Au heterostructure array has been prepared. The localized surface plasmon resonance coupling effect of the CuS@Au heterostructure array can amplify the ECL signal of EuBBN significantly. The EuBBN/CuS@Au heterostructure array-based sensing system has been prepared for the detection of miRNA-128 with a wide linear range from 1 fM to 1 nM and a detection limit of 0.24 fM. Finally, miRNA-128 in the clinic GBM tissue sample has been analysis for the distinguish of tumor grade successfully. The results demonstrated that the dual-ligand MOF/CuS@Au heterostructure array-based ECL sensor can provide important support for the development of GBM diagnosis.

Dual-functional fluorescence sensors based on 3D lanthanide metal–organic framework and its mixed matrix membrane

A new lanthanide metal–organic framework (Ln-MOF) {[Eu(DPB)(H2O)](Me2NH2+)}n (1) (H4DPB = (1,1′:3′,1′’-terphenyl)-3,3′’,5,5′’-tetracarboxylic acid）was synthesized under solvothermal conditions and presented a fascinating three-dimensional (3D) framework with 4,8-connected diamond topology, which were built from Eu3+ ions and tetra carboxylate groups. 1 showed strong red luminescence emission in the solid state at room temperature and exhibited good stability in different solvents. 1 could be used as a multi-responsive luminescent sensor for hemin and p-Nitrophenol (4-NP) with detection limits of 3.91 × 10−6 M and 1.98 × 10−4 mM, respectively. Moreover, using 1 as a filler and poly (vinylidene difluoride) (PVDF) as matrix, a mixed matrix membrane 1@PVDF was successfully prepared. 1@PVDF also exhibited fluorescence emission comparable to that of 1 and could be used for hemin and 4-NP sensing with good selectivity and remarkable recyclability.

Two-Dimensional Lanthanide Metal-Organic Framework Heterostructures for Noninvasively Photoresponsive High-Security Photonic Barcodes.

Stimuli-responsive micro/nanoscale photonic barcodes show great capacity for encryption and anticounterfeiting technologies due to multiple authentications, yet their application is commonly restricted by invasive stimuli. Herein, we report noninvasive light-stimulated high-security photonic barcodes based on spatially assembled photoresponsive two-dimensional (2D) 1,3,5-benzenetribenzoate (BTB)@Ln-MOF host-guest heterostructures. The photoluminescence (PL) spectra information on BTB@Ln-MOF heterostructures could be precisely controlled by the different wavelengths of ultraviolet (UV) light trigger. By using the PL properties and 2D heterostructures as cryptographic primitives, spatially resolved smart photonic barcodes based on both spectral and graphical coding are realized in BTB@Ln-MOF host-guest materials. These results will pave an avenue for the development of smart stimuli-responsive photonic barcodes for anticounterfeiting applications.

Lanthanide metal-organic framework-based surface molecularly imprinted polymers ratiometric fluorescence probe for visual detection of perfluorooctanoic acid with a smartphone-assisted portable device

Perfluorooctanoic acid (PFOA) poses a threat to the environment and human health due to its persistence, bioaccumulation, and reproductive toxicity. Herein, a lanthanide metal-organic framework (Ln-MOF)-based surface molecularly imprinted polymers (SMIPs) ratiometric fluorescence probe (Eu/Tb-MOF@MIPs) and a smartphone-assisted portable device were developed for the detection of PFOA with high selectivity in real water samples. The integration of Eu/Tb MOFs as carriers not only had highly stable multiple emission signals but also prevented deformation of the imprinting cavity of MIPs. Meanwhile, the MIPs layer preserved the fluorescence of Ln-MOF and provided selective cavities for improved specificity. Molecular dynamics (MD) was employed to simulate the polymerization process of MIPs, revealing that the formation of multiple recognition sites was attributed to the establishment of hydrogen bonds between functional monomers and templates. The probe showed a good linear relationship with PFOA concentration in the range of 0.02–2.8 μM, by giving the limit of detection (LOD) of 0.98 nM. Additionally, The red-green-blue (RGB) values analysis based on the smartphone-assisted portable device demonstrated a linear relationship of 0.1–2.8 μM PFOA with the LOD of 3.26 nM. The developed probe and portable device sensing platform exhibit substantial potential for on-site detecting PFOA in practical applications and provide a reliable strategy for the intelligent identification of important targets in water environmental samples.

Luminescent metal-organic framework sensor for detection of biomarker 2-thiothiazolidine-4-carboxylic acid

Using terephthalic acid (BDC) as the organic ligand and zirconium chloride (ZrCl4) as the metal source, a lanthanide metal-organic framework (Tb/Zr-UiO-66) with excellent luminescence properties was successfully prepared by introducing the lanthanide ion Tb3+in situ through a simple one-pot hydrothermal reaction, which was designed as an optical biosensor for 2-thiothiazolidine-4-carboxylic acid (TTCA), the urinary biomarker of human exposure to carbon disulfide (CS2). The fabricated Tb/Zr-UiO-66 exhibits high chemical and luminescent stability, making it competent for recognizing TTCA in aqueous environments. Significantly, its luminescence intensity change shows a good linearity relationship with the concentration of TTCA in the range of 0–110 µM, with a limit of detection (LOD) as low as 0.14 µM. Meanwhile, this sensor exhibits good selectivity and anti-interference ability towards TTCA among the various coexisting components in urine (Na+, K+, NH4+, SO42−, Cl −, creatine, creatinine, glucose, urea, etc.), and can quickly respond to TTCA within 2 min. The analysis results of powder X-ray diffraction (PXRD), fluorescence lifetime and ultraviolet–visible (UV–vis) spectrum demonstrate that the sensing mechanism can be ascribed to the competition absorption effect between TCAA and Tb/Zr-UiO-66. This biosensor with simple synthesis, stable framework, high sensitivity and selectivity, and rapid response has potential to become a powerful tool for diagnosing diseases associated with CS2 exposure.

Reticular Rare-Earth Metal–Organic Frameworks with High Stability and Defective Sites: Post-Functionalization for Hydrogen Peroxide Detection

Reticular Rare-Earth Metal–Organic Frameworks with High Stability and Defective Sites: Post-Functionalization for Hydrogen Peroxide Detection

Rare-Earth Metal-Organic Framework with Nonplanar Porphyrin Groups for High-Efficiency Photocatalysis.

Nonplanar porphyrins play crucial roles in many biological processes and chemical reactions as catalysts. However, the preparation of artificial nonplanar porphyrins suffers from complicated organic syntheses. Herein, we present a new rare-earth porphyrinic metal-organic framework (RE-PMOF), BUT-233, which is a three-dimensional (3D) framework structure with the flu topology consisting of 4-connected BBCPPP-Ph ligands H4BBCPPP-Ph = 5',5⁗-(10,20-diphenylporphyrin-5,15-diyl)bis([1,1':3',1″-terphenyl]-4,4'' dicarboxylic acid) and 8-connected Eu6 clusters. Noteworthily, the porphyrin cores of the BBCPPP-Ph ligands in BUT-233 are nonplanar with a ruffle-like conformation. In contrast, the porphyrin core in the free ligand H4BBCPPP-Ph is in a nearly ideally planar conformation, as confirmed by its single-crystal structure. BUT-233 is microporous with 6-8 Å pores and a Brunauer-Emmett-Teller (BET) surface area of 649 m2/g, as well as high stability in common solvents. The MOF was used as a photocatalyst for the oxidation degradation of a chemical warfare agent model molecule CEES (CEES = 2-chloroethyl ethyl sulfide) under the light-emitting diode (LED) irradiation and an O2 atmosphere at room temperature. CEES was almost completely converted into its nontoxic light-oxidized product CEESO (CEESO = 2-chloroethyl ethyl sulfoxide) in only 5 min with t1/2 = 2 min (t1/2: half-life). Moreover, the toxic deep-oxidized product 2-chloroethyl ethyl sulfone (CEESO2) was not detected. The catalytic activity of BUT-233 was high in comparison with those of some previously reported MOF catalysts. The results of photo/electrochemical property studies suggested that the high catalytic activity of BUT-233 was benefited from the presence of nonplanar porphyrin rings on its pore surface.

Fast fluorescence sensing of aflatoxin B1 employing a europium metal–organic framework avoiding self-fluorescence interference of target

Aflatoxin B1 (AFB1) easily contaminates grain, oil, and their products, and is strongly carcinogenic. Therefore, rapid, efficient and sensitive detection of aflatoxin plays a key role in the food industry. Here, we prepared a lanthanide metal-organic framework termed Eu-TCPP, in which the ligand can effectively sensitize Eu3+ with excellent photoluminescence properties. It is worth mentioning that the fluorescence intensity of Eu-TCPP is at 617 nm, which can avoid the interferences of AFB1 self-fluorescence emitting in the range of 400 nm–500 nm. Eu-TCPP can efficiently detect AFB1 without using antibody or biomolecular modifications, exhibiting a rapid response of 60 seconds and a limit of detection (LOD) at 11.63 ppb. The Eu-TCPP sensor also has satisfactory performance for determining AFB1 sensitively in real oil samples. In addition, the mechanism of the excellent detection performance of Eu-TCPP has been investigated using density-functional theory (DFT) calculations combined with experimental analysis. The results show that the LUMO energy level of the ligand is higher than that of the aflatoxin, which causes the electrons transfer toward the targets, and results in the reduction of the fluorescence intensity. Therefore, our proposed Eu-MOF materials based on the "antenna effect" have great potential for the development of simple, fast, and sensitive small-molecule sensors, and offer a promising prospect in POCT applications.

Construction of a novel Eu-MOF material based on different detection mechanisms and its application in sensing pollutants aniline, F- and Hg2+

Aniline is an organic pollutant with carcinogenicity and teratogenicity, while F- and Hg2+ are toxic ions that are easily soluble in water. When they are released to the environment, they will pose a threat to human health. Designing a material that can simultaneously detect three types of pollutants is of great significance. In this paper, a novel rare earth metal organic framework material (Eu-MOF) with three-dimensional structure based on 1-methylimidazole-4,5-dicarboxylic acid was synthesized for the first time through solvent thermal method. It has excellent luminescent performance and can be used as a multifunctional fluorescent probe to detect aniline, F-, and Hg2+ based on photoinduced electron transfer, energy competitive absorption, and ion exchange mechanisms, with detection limits of 1.79 × 10-8, 8.13 × 10-8, and 8.83 × 10-7 M, respectively. It is worth noting that Eu-MOF can detect F- and Hg2+ in real water samples, such as lake water and green tea water, with favorable recovery rates.

An electrochemiluminescence sensor based on lanthanide bimetallic MOFs with a “cascade sensitization mechanism” for the sensitive detection of CA242

Lanthanide metal-organic frameworks (Ln-MOFs) broaden the optical sensing applications of lanthanide ions due to the antenna effect between organic ligands and metals. However, the sensitization ability of the ligand to metal ions is limited, and maximizing the sensitization of the electrochemiluminescence behavior of Eu3+ is still a challenge for the application of Ln-MOFs. Therefore, under the guidance of the “cascade sensitization mechanism” based on the antenna effect sensitizing the electrochemiluminescence of bimetallic Ln-MOFs, we proposed Eu/Tb-MOFs with high luminescence intensity as a signal probe. According to the antenna effect, the conjugated structure and high extinction coefficient of the benzene ring of 2-amino terephthalic acid (NH2-BDC) can enhance the ECL luminescence intensity of Eu/Tb-MOFs. Tb3+ can act as an energy bridge between NH2-BDC and Eu3+, buffering the energy gap. The bimetallic sensitization is formed between Tb3+ and Eu3+, which can inhibit the reverse internal flow of energy and ensure the high luminous efficiency of Eu3+. In addition, the nanosphere mixed valence Fe3O4 as a co-reactant accelerator promotes the formation of transient free radical SO4•- through the valence change of Fe2+/Fe3+. The ECL immunosensor constructed by luminophores Eu/Tb-MOFs and nanosphere Fe3O4 provided a new explanation for the ECL self-luminous of Eu/Tb-MOFs.

Integration of lanthanide MOFs/methylcellulose-based fluorescent sensor arrays and deep learning for fish freshness monitoring

Preserving fish meat poses a significant challenge due to its high protein and low fat content. This study introduces a novel approach that utilizes a common type of lanthanide metal-organic frameworks (Ln-MOFs), EuMOFs, in combination with 5-fluorescein isothiocyanate (FITC) and methylcellulose (MC) to develop fluorescent sensor arrays for real-time monitoring the freshness of fish meat. The EuMOF-FITC/MC fluorescence films were characterized with excellent fluorescence response, ideal morphology, good mechanical properties, and improved hydrophobicity. The efficacy of the fluorescence sensor array was evaluated by testing various concentrations of spoilage gases (such as ammonia, dimethylamine, and trimethylamine) within a 20-min timeframe using a smartphone-based camera obscura device. This sensor array enables the real-time monitoring of fish freshness, with the ability to preliminarily identify the freshness status of mackerel meat with the naked eye. Furthermore, the study employed four convolutional neural network (CNN) models to enhance the performance of freshness assessment, all of which achieved accuracy levels exceeding 93 %. Notably, the ResNext-101 model demonstrated a particularly high accuracy of 98.97 %. These results highlight the potential of the EuMOF-based fluorescence sensor array, in conjunction with the CNN model, as a reliable and accurate method for real-time monitoring the freshness of fish meat.

Four Lanthanide(III) Metal-Organic Frameworks Fabricated by Bithiophene Dicarboxylate for High Inherent Proton Conduction.

Currently, it is still a challenge to directly achieve highly stable metal-organic frameworks (MOFs) with superior proton conductivity solely through the exquisite design of ligands and the attentive selection of metal nodes. Inspired by this, we are intrigued by a multifunctional dicarboxylate ligand including dithiophene groups, 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid (H2DTD), and lanthanide ions with distinct coordination topologies. Successfully, four isostructural three-dimensional lanthanide(III)-based MOFs, [Ln2(DTD)3(DEF)4]·DEF·6H2O [LnIII = TbIII (Tb-MOF), EuIII (Eu-MOF), SmIII (Sm-MOF), and DyIII (Dy-MOF)], were solvothermally prepared, in which the effective proton transport will be provided by the coordinated or free solvent molecules, the crystalline water molecules, and the framework components, as well as a large number of highly electronegative S and O atoms. As expected, the four Ln-MOFs demonstrated the highest proton conductivities (σ) being 0.54 × 10-3, 3.75 × 10-3, 1.28 × 10-3, and 1.92 × 10-3 S·cm-1 for the four MOFs, respectively, at 100 °C/98% relative humidity (RH). Excitingly, Dy-MOF demonstrated an extraordinary ultrahigh σ of 1 × 10-3 S·cm-1 at 30 °C/98% RH. Additionally, the plausible proton transport mechanisms were emphasized.

A smartphone sensing platform for the sensitive and selective detection of clothianidin based on MIP-functionalized lanthanide MOF.

Anovel molecularly imprinted nanomaterial (Eu (BTC)-MPS@MIP) was synthesized on the surface of silanized europium-based metal-organic frameworks (Eu (BTC)-MPS) using 1, 3, 5-benzotrioic acid (H3BTC) as a ligand. The resulting Eu (BTC)-MPS@MIP was applied to constructing a smartphone sensing platform for the sensitive and selective detection of clothianidin (CLT) in vegetables. The synthesized Eu (BTC)-MPS@MIP demonstrated the successful formation of a typical core-shell structure featuring a shell thickness of approximately 70 - 80nm. The developed sensing platform based on Eu (BTC)-MPS@MIP exhibited sensitivity in CLT detection with a detection limit of 4µg/L and a linear response in the range 0.01 - 10mg/L at excitation and emission wavelengths of 365nm and 617nm, respectively. The fluorescence sensing platform displayed excellent specificity for CLT detection, as evidenced by a high imprinting factor of 3.1. This specificity is primarily attributed to the recognition sites in the molecularly imprinted polymer (MIP) layer. When applied to spiked vegetable samples, the recovery of CLT ranged from 78.9 to 102.0%, with relative standard deviation (RSD) values falling between 2.2 and 6.2%. The quenching mechanism of Eu (BTC)-MPS@MIP toward CLT can be attributed to the inner filter effect (IFE), resulting from the optimal spectral overlap between the absorption spectrum of CLT and the excitation spectra of Eu (BTC)-MPS@MIP. The proposed method has the potential for extension to the detection of other pesticides by replacing the MIP recognition probes.

Introduction of functionality into a Tb(III)-organic framework via mixed-ligand strategy for selective C2H2 capture and ratiometric Cr(VI) detection

Introduction of porosity and fluorescent properties into lanthanide metal–organic frameworks (MOFs) with rational design to achieve multifunctional use is of great significance from the energy and environmental viewpoint. In this study, a microporous Tb(III)-based MOF with the formula of {[Tb2(oba)3(Phen)2](DMF)2(H2O)4}n (1) was solvothermally prepared via using the mixed ligands of 1,10-phenanthroline (Phen) and 4,4′-oxybis(benzoic acid) (H2oba) as organic connecters. The structural evaluation results indicate that complex 1 is composed of binuclear Tb2(CO2)6(Phen)2 clusters which are extended by the oba2− ligands to afford a two-fold interpenetrated framework with one-dimensional microporous channels along the b-axis. Gas sorption studies show that the activated 1 demonstrates a high ideal adsorption solution theory (IAST) sorption selectivity of 7.4 toward C2H2 in a C2H2/CO2 gas mixture, which are further supported by the dynamic breakthrough experiments. The grand canonical Monte Carlo (GCMC) simulation results indicate that the synergistic effects of the H-bond interactions of C2H2 with oba2− ligands and the C–H···π interactions with Phen ligand contribute to the strong binding of the framework toward C2H2 molecules. What's more, the luminescent measurements reveal that the emission of 1 features both the characteristic peaks of Phen ligand and Tb(III) ion, which could be further applied as a self-calibrating sensor for the Cr(VI) detection in water. To the best of our knowledge, complex 1 represents the first example of Tb-MOF holding such a high C2H2/CO2 selectivity together with ratiometric Cr(VI) detection performances.