Lewis Base Centers Research Articles

Unraveling Lewis acid-base sites in defected MOFs for catalyzing dicyclopentadiene hydrogenation via a DFT study and descriptor exploration

The 12-connected UiO-66 MOFs with great defect regulation ability have attracted significant attention due to the easily tunable electronic structure and surface electrostatic potential distribution of metal nodes. In this density functional theory (DFT) study, we systematically explored the effect of bi-active site types as the frustrated Lewis pair (FLP) and classical Lewis pair (LP) as well as metal elements of secondary building units (SBUs) on the catalytic hydrogenation of dicyclopentadiene (DCPD) to tetrahydrodicyclopentadiene (THDCPD). These design strategies effectively modulate the frontier molecular orbital energy level that determines the binding strength between MOFs and adsorbed species *Hδ+-Hδ- and charges transfer before and after H2 chemisorption. We also found that the heterolytic H2 adsorption energy and charges transfer linearly correlate with the energy barrier. In order to unravel the clear-cut designing strategies and further simplify computational complexity, we firstly proposed the ADCH charges difference between the Lewis acid and the Lewis base centers (ΔQM-O) as an intrinsic descriptor for catalytic activity of DCPD into THDCPD, which can effectively describe the reactivity and electrostatic effects of oppositely charged bi-active sites in the system. Furthermore, the defective UiO-66(Ce) MOF with moderate ΔQM-O effectively balance the contradiction between the barriers of two primitive reaction: the heterolytically H2 dissociation to *Hδ+-*Hδ- and the desorption of the active hydrogen species to hydrogenate 8,9-dihydrodicyclopentadiene (8,9-DHDCPD), resulting in the optimal catalytic performance. This work provides a deep understanding of the catalytic mechanism of MOFs with multiple active sites and might open up avenues for the rational design of novel hydrogenation catalysts.

Density functional theory study on frustrated Lewis pairs catalyzed C‐H activation of heteroarenes: Mechanism variation tuning by electronic effect

AbstractUnreactive C‐H bond activation is a new horizon for frustrated Lewis pairs (FLPs) chemistry. Although concerted mechanism (Science 2015, 349, 513) and stepwise carbene mechanism (Org. Lett. 2018, 20, 1102) have been proposed for the FLPs catalyzed C‐H bond activation of 1‐methylpyrrole, the influence of electronic properties of FLPs on the reaction mechanism is far away from well‐understood. In this study, an assortment of P‐B type FLPs with different electronic characteristic was employed to study the catalyzed C‐H bond activation of 1‐methylpyrrole by using density functional theory calculations. Detailed calculations demonstrated that the reactivity variation and the reaction mechanism binary of FLPs catalyzed C‐H activation can be varied by tuning electronic effect of Lewis base center. On the one hand, the concerted C‐H activation reactivity is mainly controlled by the electron donation of the lone pair of Lewis base center; thus, the FLPs with electron‐donating substituents (FLP1, FLP2, and FLP3) catalyzed the C‐H bond activation through concerted mechanism. On the other hand, the reactivity of stepwise carbene mechanism is mostly attributed to the vacant orbital of Lewis acid center; as a result, the FLP5 bearing ‐P(C6F5)2 preferred to catalyzed the bond activation through concerted mechanism. In contrast, a metathesis mechanism through strained four‐membered ring transition state is less feasible. These results should provide deeper insight and broader perspective to understand the structure and function of FLPs for rational design of FLPs catalyzed C‐H bond activation.

Resourcification of CO2 to high-value-added glycerol carbonate by ZnAlCe composite oxides with frustrated Lewis pairs

Zinc-aluminum-cerium composite oxide (ZnAlCe) catalysts were prepared by co-precipitation to catalyze the direct synthesis of glycerol carbonate (GC) from carbon dioxide (CO2) and glycerol. The characterization results showed that the lattice oxygen served as Lewis basic centers and Ce4+ served as Lewis acidic centers on Zn4AlCe catalyst, and frustrated Lewis pairs (FLPs) were formed due to the steric hindrance in the catalyst structure. CO2 was easily activated by FLPs because the acidic and basic centers of FLPs bound to the oxygen and carbon atoms of CO2, respectively. The experimental results indicated that Zn4AlCe catalyst presented excellent catalytic performance with good thermal stability and strong regeneration ability. Under the reaction conditions of 0.115 g catalyst, 12 h, 170 °C, 4.5 MPaCO2 and 5 mL acetonitrile dosage, the GC yield and selectivity were 28.9 % and 51.0 %, respectively. The GC yield is relatively high among similar catalysts reported so far, which lays the foundation for future industrial considerations.

4-Fluorobenzyl cyanide, a sterically-hindered solvent expediting interfacial kinetics in lithium-ion batteries.

The electrochemical performance of lithium-ion batteries (LIBs) is plagued by sluggish interfacial kinetics. Fortunately, the Li+ solvation structure bridges the bulk electrolyte and interfacial chemistry, providing a pathway for promoting electrochemical kinetics in LIBs. Herein, we improve the interfacial kinetics by tuning the Li+ coordination chemistry based on solvent molecular engineering. Specifically, 4-fluorobenzyl cyanide (FBCN), featuring steric hindrance and a weak Lewis basic center, is designed to construct a bulky coordination structure with Li+, weakening ion-dipole interaction (Li+-solvents) but promoting coulombic attraction (Li+-anions) at a normal Li salt concentration. This sterically-controlled solvation chemistry reduces the interfacial barrier and thus contributes to improved rate performance, as demonstrated practically in LiFePO4//graphite pouch cells. This study provides fresh insights into solvent steric control and coordination chemistry engineering, opening a new avenue for enhancing electrochemical kinetics in LIBs.

Metal-organic framework-based nanomaterials for CO2 storage: A review.

The increasing recognition of the impact of CO2 emissions as a global concern, directly linked to the rise in global temperature, has raised significant attention. Carbon capture and storage, particularly in association with adsorbents, has occurred as a pivotal approach to address this pressing issue. Large surface area, high porosity, and abundant adsorption sites make metal-organic frameworks (MOFs) promising contenders for CO2 uptake. This review commences by discussing recent advancements in MOFs with diverse adsorption sites, encompassing open metal sites and Lewis basic centers. Next, diverse strategies aimed at enhancing CO2 adsorption capabilities are presented, including pore size manipulation, post-synthetic modifications, and composite formation. Finally, the extant challenges and anticipated prospects pertaining to the development of MOF-based nanomaterials for CO2 storage are described.

In-situ construction of ionic ultramicroporous metal–organic frameworks for high-efficiency CO2/CH4 separation

The high-efficiency capture of CO2 from biogas by adsorption is highly desirable, which, yet faces the challenges regards of the unsatisfactory adsorption efficiency, selectivity, and regeneration performance. Herein, ionic ultramicroporous metal organic frameworks (IUM-MOFs) with high CO2 affinity are constructed by one-step in-situ coordination strategy and used for CO2/CH4 separation. The phenoxylate anion-functionalized ionic liquid (FIL) serves as competitive ligands in the formation of IUM-MOFs. The oxyl group exhibits high affinity with CO2 as the Lewis basic center, while the rigid counterion occupies the adsorption space of CH4 in the cavities of IUM-MOFs, thus bringing about superior CO2 adsorption capacity of 149 cm3 g−1 (150% higher than that of Cu-BTC) and high IAST predicted selectivity with CH4 of 22 under atmospheric condition. Mechanism analysis demonstrated that the formation of hydrogen bonds between CO2 with coordinated IL and H2O and IL-enhanced polarity of MOFs benefit to the CO2 adsorption. In addition, the IUM-MOFs could be facilely regenerated at 120 °C with favorable recycling stability. This work provides facile strategy for the rational design of IUM-MOFs and lays useful insights for structural tuning to promote their applications.

Multistep Cascade Catalytic Reactions Employing Bifunctional Framework Compounds.

Multistep cascade reactions are important to achieve atom as well as step economy over conventional synthesis. This approach, however, is limited due to the incompatibility of the available reactive centers in a catalyst. In the present study, new MOF compounds, [Zn2(SDBA)(3-ATZ)2]·solvent, I and II, with tetrahedral Zn centers as good Lewis acidic sites and the free amino group of the 3-amino triazole ligand as a strong Lewis base center were shown to perform 4-step cascade/tandem reaction in a facile manner. Effective conversion of benzaldehyde dimethyl acetal in the presence of excess nitromethane at 100 °C in water to 1-(1,3-dinitropropan-2-yl) benzene was achieved in 10 h with yields of ∼95% (I) and ∼94% (II). This 4-step cascade reaction proceeds via deacetalization (Lewis acid), Henry (Lewis base), and Michael (Lewis base) reactions. The present work highlights the importance of spatially separated functional groups in multistep tandem catalysis─the examples of which are not common.

Synthesis of a Carbene-Stabilized (Diphospha)aminyl Radical and Its One Electron Oxidation and Reduction to Nonclassical Nitrenium and Amide Species

Herein, we report the synthesis of an acyclic carbene-stabilized diphospha(aminyl) PNP radical CAACMePNPCAACMe 4 (CAACMe = 1-[2,6-bis(isopropyl)phenyl]-3,3,5,5-tetramethyl-2-pyrrolidinylidene) by a facile one-pot, seven-electron reduction of hexachlorophosphazene chloride [Cl3PNPCl3][Cl]. The PNP radical 4 features a conjugated framework with spin density primarily localized on the central nitrogen atom as well as the flanking carbenes. Unlike other tripnictogen radicals, 4 undergoes facile one-electron oxidation and reduction to yield nonclassical nitrenium and amide species [5]+ and [6]-, respectively. The cation [5]+ exhibits conformational flexibility in the solution state between the expected W-shaped geometry [5b]+ and a previously unobserved linear heteroallene-type structure [5a]+, which was characterized in the solid state. The equilibrium was explored both computationally and experimentally, showing that [5a]+ is favored over [5b]+ both enthalpically (ΔH = -2.9 × 103 ± 80 J mol-1) and entropically (ΔS = 4.2 ± 0.25 J mol-1 K-1). The formal amide [6]- displays remarkable flexibility in its coordination chemistry due to the presence of multiple Lewis basic centers, as evidenced by the structure of its potassium complex K262, which exhibits μ, κ-P, κ-P, and η3-PNP coordination modes. Protonation of [6]- leads to the formation of an amine 7, which features a trigonal planar geometry around nitrogen.

Computational Design of Frustrated Lewis Pairs as a Strategy for Catalytic Hydrogen Activation and Hydrogenation Catalyst.

Catalytic hydrogenation is one of the most important reaction types commonly used in chemistry and chemical industry. Recently, there has been significant interest in developing a metal-free hydrogenation catalyst to avoid the problems caused by using heavy transition metal catalysts. On the basis of the advances of metal-free hydrogen activation with frustrated Lewis pairs (FLPs, e.g. tBu3P/B(C6F5)3) which often uses boron as a Lewis acid center, we computationally explored the prospect for phosphorus(V) and sulfur(VI) as Lewis acid centers to construct FLPs for hydrogen activation and hydrogenation. We found out that the proposed FLPs with P(V)- or S(VI)-centered Lewis acid can also activate H2 with a mechanism similar to that used by the conventional FLPs. A heterolytic cleavage of H-H is achieved when electrons are donated simultaneously from the σ orbital of H2 to the empty orbital of the Lewis acid center and from the lone-pair orbital of the Lewis base center to the σ* orbital of H2. The multiple C-H···F hydrogen bonds further aid the association of the pairs for H2 activation. Some of our designed FLPs possess kinetics and thermodynamics for developing hydrogenation catalysts. This computational exploration could inspire experimental development of a new type of FLPs with P(V) or S(VI) or a Lewis acid partner for FLPs for reversible H2 activation.

Influence of the Element and Substituent Effects on the Reactivity of Catching Reactions of Difluorocarbene by Benzene-Bridged and Group-13/Group-15-Based Frustrated Lewis Pairs

The trapping reactions of CF2 by benzene-bridged Group-13/P-based and B/Group-15-based frustrated Lewis pairs (FLPs) have been computationally investigated based on density functional theory. Interestingly, our theoretical calculations predict that the capture of CF2 by all five Group-13/P-based FLPs is energetically feasible. However, in the B/Group-15-based FLPs, only the phosphorus-based B/P-FLP can trap CF2 from kinetic and thermodynamical viewpoints. According to the analyses of the activation strain model, it can be known that the atomic radius of the G15 element (Lewis base) of benzene-bridged B/Group-15-FLP plays an important role in controlling the reactivity of the CF2 catching reactions, whereas the atomic radius of the Group-13 center (Lewis acid) does not play a role in influencing the activation barrier of these CF2 catching reactions. Our theoretical findings based on sophisticated methods suggest that the forward bonding is the FLP-to-CF2 interaction, the LP (Group-15-donor) → vacant p-π-orbital (CF2), which was quantitatively proved to be strong in such present CF2 catching reactions. However, the back bonding is the CF2-to-FLP interaction, the empty σ-orbital (Group-13-acceptor) ← sp2-σ-orbital (CF2), which was verified to be relatively weak. Our theoretical pieces of evidence reveal that the stronger electron-donating ability of the substituents is attached to the Lewis basic center and can make the reaction barrier of the benzene-bridged Group-13/Group-15-based FLP-related compound catching CF2 smaller and more exothermic.

Bifurcated Chalcogen Bonds Based on One σ-Hole

Chalcogen bonds are noncovalent interactions and are increasingly coming into focus for the design of complex structures in research areas such as crystal engineering, molecular recognition and catalysis. Conceptionally, chalcogen bonds can be considered as interaction between one σ-hole and one Lewis base center. Herein, we analyze the interaction between bidentate chelating ligands having two nucleophilic centers with one single σ-hole of a chalcogenazole (two-lone-pair/one-σ-hole interactions). Referring to this, we show by quantum chemical calculations and X-ray studies that three bond types are possible: in the first case, a chalcogen bond is formed between the σ-hole and only one of the Lewis base centers. In the second case, a strong bond is formed by one nucleophilic center; the second center provides only a small amount of additional stabilization. In the third case, two equivalent bonds to the σ-hole are formed by both Lewis base centers. According to the calculations, the bifurcated bonds are stronger than simple chalcogen bonds and lead to a more rigid molecular arrangement in the complex.

Asymmetric Intramolecular Hydroalkoxylation of 2‐Vinylbenzyl Alcohols with Chiral Boro‐Phosphates

AbstractAsymmetric intramolecular hydroalkoxylation of alkenes represents a very important approach to access optically active cyclic ethers. It was found that B(C6F5)3 could catalyze the cyclization of 2‐vinylbenzyl alcohols with only 0.05 mol % catalyst loading, affording the desired product in high yields. To accomplish the asymmetric reaction, a novel type of chiral boro‐phosphates was developed by treating chiral phosphoric acid with Piers’ borane, in which the oxygen atom of P=O and the boron atom act as Lewis base and acid centers, respectively. A highly enantioselective hydroalkoxylation was successfully realized to give optically active 1,3‐dihydroisobenzofuran derivatives in 78–99 % yields with 60–97 % ee's, in which an activation of O−H bond of alcohols by the boro‐phosphate species is hypothesized.

Asymmetric Intramolecular Hydroalkoxylation of 2-Vinylbenzyl Alcohols with Chiral Boro-Phosphates.

Asymmetric intramolecular hydroalkoxylation of alkenes represents a very important approach to access optically active cyclic ethers. It was found that B(C6 F5 )3 could catalyze the cyclization of 2-vinylbenzyl alcohols with only 0.05 mol % catalyst loading, affording the desired product in high yields. To accomplish the asymmetric reaction, a novel type of chiral boro-phosphates was developed by treating chiral phosphoric acid with Piers' borane, in which the oxygen atom of P=O and the boron atom act as Lewis base and acid centers, respectively. A highly enantioselective hydroalkoxylation was successfully realized to give optically active 1,3-dihydroisobenzofuran derivatives in 78-99 % yields with 60-97 % ee's, in which an activation of O-H bond of alcohols by the boro-phosphate species is hypothesized.

Synergetic charge transfer from Ti[sbnd]O2− basic centers at Li4Ti5O12 spinel surface

Interfacial chemistry plays an important role in understanding electrode process kinetics of many chemical reactions, e.g. photocatalyst, electrocatalyst, and electrochemistry. In this context, a systematic investigation is conducted to reveal the mechanism of electrode-electrolyte interface between Li4Ti5O12 (LTO) spinel and electrolyte molecule, aiming to tackle the notorious package swelling issue in rechargeable batteries. Using the gas chromatography–mass spectrometry and electron microscopy techniques, the interplays between the LTO and dimethyl carbonate (DMC) are uncovered to be a synergetic chemical catalytic process involving the truncated oxygens of the surface TiO dangling bonds, which are negatively polarized as the catalytic centers with the strong Lewis basicity. The Lewis basic centers catalyze the nucleophilic substitution of DMC with only trace amounts of water, resulting in the gaseous products, such as CO2 and methanol. These findings deepen the understandings on the fundamental chemistry and catalysis of solid-liquid interfaces, especially the metal oxide-organic interfaces.

N/O→B dative bonds supplemented by N-HN/HC hydrogen bonds make BN-cages an attractive candidate for DNA-nucleobase adsorption - an MP2 prediction.

The response of B12N12-nanocages towards DNA-nucleobases (adenine, guanine, cytosine, and thymine) is investigated using MP2 and DFT (M06-2X) levels of theory with the 6-311+G** basis set. Multiple BN-cage-nucleobase structures for each nucleobase emerged depending on the number of Lewis base centers of nucleobases. The main source of stability of these complexes is the N/O→B dative bond, where the N or O atom of nucleobases donates the lone-pair electron to one of the boron atoms of the nanocage. Nitrogen atoms of the BN-cage, adjacent to the B-site forming dative bond, act as a proton acceptor to form multiple (N-HN and N-HC) hydrogen bonds, where proton-donors NH and CH are part of nucleobases. MP2/6-311+G** adsorption energies are -43.1, -43.4 and -45.3 kcal mol-1 (B12N12-adenine), -37.1, -41.9 and -43.3 kcal mol-1 (B12N12-guanine), -41.3 and -43.4 (B12N12-cytosine), and -29.3 and -31.3 (B12N12-thymine). Similar adsorption energies were recorded for larger BN-fullerenes-nucleobases, namely B16N16 and B24N24. Changes in adsorption energies and structures of these nano-bio-hybrid materials in aqueous media are also discussed. Computationally cost-effective MP2 single point calculations at the M06-2X optimized geometries were found to be reliable in predicting adsorption energies. The effect of the BN-network and H-bonds on the adsorption process is assessed by comparing the results with simple BH3-nucleobase models. BSSE correction to the adsorption energy is not recommended.

Cyclic Ether Triggers for Polymeric Frustrated Lewis Pair Gels.

Sterically hindered Lewis acid and base centers are unable to form Lewis adducts, instead forming frustrated Lewis pairs (FLPs), where latent reactivity can be utilized for the activation of small molecules. Applying FLP chemistry into polymeric frameworks transforms this chemistry into responsive and functional materials. Here, we report a versatile synthesis strategy for the preparation of macromolecular FLPs and explore its potential with the ring-opening reactions of cyclic ethers. Addition of the cyclic substrates triggered polymer network formation, where the extent of cross-linking, strength of network, and reactivity are tuned by the steric and electronic properties of the ethers. The resultant networks behave like covalently cross-linked polymers, demonstrating the versatility of FLPs to simultaneously tune both small-molecule capture and mechanical properties of materials.

Characterization of IR spectroscopy, APT charge, ESP maps, and AIM analysis of C20 and its C20‐nAln heterofullerene analogous (n = 1–5) using DFT

AbstractIn this computational inspection, influences of substituted aluminum(s) on the vibrational frequency, infrared (IR) spectroscopy, atomic polar tensor (APT) charge, and electrostatic potential (ESP) map, along with atoms in molecules (AIM) analysis of C20 fullerene and its C20‐nAln derivatives (where n = 1–5) are investigated using B3LYP/6‐311 + G*, B3LYP/6‐311++G**, M06‐2X/6‐311++G**, B3PW91/6‐311 + G*, and B3LYP/AUG‐cc‐pVTZ. IR spectroscopy emerges that exclusive of C15Al5, the other optimized structures are global minimum without imaginary frequency. Substituting C20 to C20‐nAln heterofullerenes leads to higher APT charge distribution upon surfaces of heterofullerenes than unsubstituted species. Accordingly, the highest negative and positive APT charges on carbon and aluminum atoms of C15Al5 suggest that these sites can be attacked more readily by electrophilic and nucleophilic regents, that is, may act as the Lewis acid or Lewis base centers. This species is including five alternative aluminum heteroatoms in equatorial position and can be suitable hydrogen storage. AIM analysis of the studied C20‐nAln derivatives implies the highest ρ(r) of 0.083 a.u., the highest negative ∇2ρ(r) of −0.084 and −0.085 a.u. and the highest positive G(r)/V(r) of 4.86 and 4.69 a.u. at bond critical point of CAl bond with the strongest covalent property in the most stable C19Al1 and C17Al3 species, respectively, between studied structures.

A New Tb(III) MOF for Selective Detection of Cu2+ Ion and Prevention Ability Against Staphylococcus aureus Biofilm Formation on Patients with Renal Failure

In the present study, a new fluorescent Tb(III)-based coordination polymer (CP) with the chemical formula of [Tb(TCPB)(DMF)3]n (1) has been presented via using a mixed-donor ligand 1,3,5-tris(1-(2-carboxyphenyl)-1H-pyrazol-3-yl)benzene (H3TCPB) under the solvothermal reaction conditions. CP 1 becomes the predominated selection for luminescence probing experiments because of the highly developed stability in watery reagent and Lewis basic centers. Furthermore, the prevention ability of the synthetic compound against bacterial infection induced by Staphylococcus aureus during hemodialysis with renal failure was evaluated. With the help of molecular docking simulation, it can be seen from the molecular level that both carboxyl and pyrazole groups on the Tb complex are responsible for the binding interactions and therefore they are the origin of biological activities.

Multisite Coordination Ligands on Cyclotriphosphazene Core for the Assembly of Metal Clusters and Porous Coordination Polymers

AbstractIn this review, we account the recent advancements on cyclotriphosphazene (N3P3Cl6) based multi‐site coordination ligands for the synthesis of multi‐metallic architectures. In case of N3P3Cl6, Phosphorous centres with two chlorides use to be bonded with nitrogen [−P(Cl2)=N−]3 at alternative positions in six membered ring to provide a robust planar structure to anchor the ligand arms with wide flexibility. Cyclic P−N robust motif is renowned as the potential support for the design of multi‐site ligands originating from phosphorus centres by viable substitution of variable number of ligand units (1 to 6) consist of one or more coordination site(s) via geminal and/or non‐geminal modes. Despite these phosphorus centres are promising to support in ligand structure, occasionally involve in coordination with transition metals as well. Three of alternative nitrogen atoms in this heterocyclic core are supposed to function as Lewis base centres while the electron releasing substituents occurred to tether on phosphorus centres, also when the resultant ring size favours adequate interaction towards the transition metal ions with respect to skeletal flexibility. The ligand modes vary with respect to numbers and orientation of coordination sites, which is imperative to enrich the ligation ability. Moreover, several examples of cyclotriphosphazene core ligands consist of the spacer oxygen atom while tethering with exocyclic ligand units to incorporate more flexibility. In accordance with coordination sites on ligand framework and choice of metal, the skeletal ring nitrogen atom(s) of the cyclotriphosphazene can be involved in coordination with metal ions. Indeed, the coordination of ligands is reported to coordinate with main group, transition and lanthanide metal ions to form variety of metal clusters and porous coordination polymers. Subsequently, the geometry of homo or heterometallic complexes with respect to versatile coordination modes of metallic complexes tends to afford inherent chemical properties for specific application. In terms of exocyclic ligands, the heterocyclic units such as pyridyloxy‐, pyrazolyl‐, pyridylalkylamino‐, bipyridyl‐, 1,10‐phenanthroline, porphyrinato, hydrazide, hydrazone, Schiff's base and spirocyclic amine units attached to cyclotriphosphazene were exploited to form series of metal complexes. Similarly, the variety of metal clusters, polymeric network (1D to 3D) and porous coordination polymers have been reported on basis of cyclic core molecule substituted with ligand units, pyridyloxy‐, multi‐carboxylic, aromatic amines substituted pyridyloxy‐ and imidazole moiety involved to form variety of products.

Lanthanide−Organic complex with uncoordinated lewis basic triazolyl sites as multi-responsive sensor for nitrobenzene, Cu2+ and MnO4−

Ln-coordination polymer {Tb(BTTA)1.5(H2O)4.5]n(Tb-1) was successfully obtained via solvo-thermal reaction of Tb(NO3)3⋅6H2O and 2,5-bis-(1H-1,2,4-triazol-1-yl) terephthalic acid (H2BTTA). The measurement of single-crystal X-ray diffraction exhibits that complex Tb-1 displays two-dimensional lay-by-lay frameworks with one-dimensional channels along b direction. Owning to its high stability in aqueous solution and organic solvent, as well as its exposed Lewis basic centers, Tb-1 was selected for luminescence probe experiments on anions, cations and organic small molecules. The results display that Tb-1 not only shows high selectivity and sensitivity for the recognition of Cu2+ and MnO4− with lower detection limits as 1.22 μM and 0.39 μM, respectively, but also exhibits high recognition ability and low detection limit (2.71 μM) for nitrobenzene (NB).