Coordinated H2O Molecules Research Articles

Regulating Spin Density using TEMPOL Molecules for Enhanced CO2-to-Ethylene Conversion by HKUST-1 Framework Derived Electrocatalysts.

The selectivity of multicarbon products in the CO2 reduction reaction (CO2RR) depends on the spin alignment of neighboring active sites, which requires a spin catalyst that facilitates electron transfer with antiparallel spins for enhanced C-C coupling. Here, we design a radical-contained spin catalyst (TEMPOL@HKUST-1) to enhance CO2-to-ethylene conversion, in which spin-disordered (SDO) and spin-ordered (SO) phases co-exist to construct an asymmetric spin configuration of neighboring active sites. The replacement of axially coordinated H2O molecules with TEMPOL radicals introduces spin-spin interactions among the Cu(II) centers to form localized SO phases within the original H2O-mediated SDO phases. Therefore, TEMPOL@HKUST-1 derived catalyst exhibited an approximately two-fold enhancement in ethylene selectivity during the CO2RR at -1.8 V versus Ag/AgCl compared to pristine HKUST-1. In situ ATR-SEIRAS spectra indicate that the spin configuration at asymmetric SO/SDO sites significantly reduces the kinetic barrier for *CO intermediate dimerization toward the ethylene product. The performance of the spin catalyst is further improved by spin alignment under a magnetic field, resulting in a maximum ethylene selectivity of more than 50 %. The exploration of the spin-polarized kinetics of the CO2RR provides a promising path for the development of novel spin electrocatalysts with superior performance.

Regulating Spin Density using TEMPOL Molecules for Enhanced CO2‐to‐Ethylene Conversion by HKUST‐1 Framework Derived Electrocatalysts

The selectivity of multicarbon products in the CO2 reduction reaction (CO2RR) depends on the spin alignment of neighboring active sites, which requires a spin catalyst that facilitates electron transfer with antiparallel spins for enhanced C‐C coupling. Here, we design a radical‐contained spin catalyst (TEMPOL@HKUST‐1) to enhance CO2‐to‐ethylene conversion, in which spin‐disordered (SDO) and spin‐ordered (SO) phases co‐exist to construct an asymmetric spin configuration of neighboring active sites. The replacement of axially coordinated H2O molecules with TEMPOL radicals introduces spin‐spin interactions among the Cu(II) centers to form localized SO phases within the original H2O‐mediated SDO phases. Therefore, TEMPOL@HKUST‐1 derived catalyst exhibited an approximately two‐fold enhancement in ethylene selectivity during the CO2RR at ‐1.8 V versus Ag/AgCl compared to pristine HKUST‐1. In situ ATR‐SEIRAS spectra indicate that the spin configuration at asymmetric SO/SDO sites significantly reduces the kinetic barrier for *CO intermediate dimerization toward the ethylene product. The performance of the spin catalyst is further improved by spin alignment under a magnetic field, resulting in a maximum ethylene selectivity of more than 50%. The exploration of the spin‐polarized kinetics of the CO2RR provides a promising path for the development of novel spin electrocatalysts with superior performance.

Tandem Chemistry with Janus Mesopores Accelerator for Efficient Aqueous Batteries.

A reliable solid electrolyte interphase (SEI) on the metallic Zn anode is imperative for stable Zn-based aqueous batteries. However, the incompatible Zn-ion reduction processes, scilicet simultaneous adsorption (capture) and desolvation (repulsion) of Zn2+(H2O)6, raise kinetics and stability challenges for the design of SEI. Here, we demonstrate a tandem chemistry strategy to decouple and accelerate the concurrent adsorption and desolvation processes of the Zn2+ cluster at the inner Helmholtz layer. An electrochemically assembled perforative mesopore SiO2 interphase with tandem hydrophilic -OH and hydrophobic -F groups serves as a Janus mesopores accelerator to boost a fast and stable Zn2+ reduction reaction. Combining in situ electrochemical digital holography, molecular dynamics simulations, and spectroscopic characterizations reveals that -OH groups capture Zn2+ clusters from the bulk electrolyte and then -F groups repulse coordinated H2O molecules in the solvation shell to achieve the tandem ion reduction process. The resultant symmetric batteries exhibit reversible cycles over 8000 and 2000 h under high current densities of 4 and 10 mA cm-2, respectively. The feasibility of the tandem chemistry is further evidenced in both Zn//VO2 and Zn//I2 batteries, and it might be universal to other aqueous metal-ion batteries.

Synthesis, characterization, and comparison of explosive hexaamminecobalt(III) and nitropentamminecobalt(III) cyclopentazolate (cyclo‐N5−) salts

AbstractMetal pentazolate hydrates have attracted attention because of the unique stabilization mechanisms of cyclo‐N5− anions during crystal stacking. However, coordinated H2O molecules influence the stability of cyclo‐N5− anion‐containing salts, and the structure‐property relationship of high‐valent cobalt pentazolate salts has not been previously reported. Werner‐type cobalt(III) cations that trap cyclo‐N5− anions, a novel class of cyclo‐N5−‐based materials, were prepared and characterized by infrared spectroscopy, elemental analysis, electrospray ionization mass spectrometry, and thermogravimetry with differential scanning calorimetry. The [Co(NH3)5(NO2)]2+ cation was also introduced via metathesis reactions to compare the intermolecular interactions in its intriguing structures. Single‐crystal X‐ray diffraction revealed extensive hydrogen bonding networks in hexaamminecobalt(III) and nitropentamminecobalt(III) cyclo‐N5− salts between cyclo‐N5− anions and NH3 ligands or nitro groups. In addition, [Co(NH3)6(N5)3] (1) and [Co(NH3)5(NO2)](N5)2 (2) exhibited relatively high nitrogen contents of 79.2 % and 67.9 %, respectively, and the impact sensitivities of 1 (IS=5 J) and 2 (IS=4 J) are comparable to that of lead azide.

Distinct magnetic relaxation behaviors in nitronyl nitroxide-based cocrystalline supramolecular system with DyIII-O-H⋯O-N hydrogen bond

The self-assembly of Dy(hfac)3·2H2O, Co(hfac)2·2H2O or Mn(hfac)2·2H2O (hfac = hexafiuoroacetylacetonate) with NITPh-triazole radical (NITPh-triazole = 2-[2-(1H-1,2,4-triazol-1-yl)phenyl]-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) produces two 2p-3d-4f compounds of formula {[Dy(hfac)3(H2O)2][Co2(hfac)4(NITPh-triazole)2]2.CH2Cl2}n (1) and {[Dy(hfac)3(H2O)2][Mn2(hfac)4(NITPh-triazole)2]2}n (2) featuring extraordinary intermolecular hydrogen bonds between coordinated H2O molecules and uncoordinated NO groups linking into a supramolecular one-dimensional chain. Notably, the LnIII-O-H⋯O-N hydrogen bond bridge has been rarely observed in nitronyl nitroxide-metal system. Magnetic performance and heat capacity of both 2p-3d-4f compounds are detected. Interestingly, 1 and 2 both show apparent double peaks of χ′′ signals with two-step magnetic relaxation processes. Furthermore, the effective barrier of 1 is obviously higher than 2. As far as we know, employing unusual intermolecular LnIII-O-H⋯O-N hydrogen bond, it is the first to obtain supramolecular 2p-3d-4f one-dimensional heterospin materials with apparent slow magnetic relaxation and heat capacity behaviors.

Reconstructing the Anode Interface and Solvation Shell for Reversible Zinc Anodes.

The attractive advantages of the Zn metal anode and water-based electrolyte, such as inherent safety and low cost, endow the zinc-ion batteries (ZIBs) with great potential in the future energy storage market. However, the severe surface side reactions and dendrites affect the service lifespan and electrochemical performance of ZIBs. Herein, a bifunctional electrolyte additive, l-ascorbic acid sodium (LAA), has been added into ZnSO4 (ZSO) electrolyte (ZSO + LAA) to settle the above issues of ZIBs. On the one hand, the LAA additive tends to adsorb on the Zn anode surface to generate a H2O-resistive passivation layer, which can effectively isolate the H2O corrosion and regulate the Zn2+ ion 3D diffusion, thus inducing a uniform deposition layer. On the other hand, the strong adsorption capacity between LAA and Zn2+ can transform the solvated [Zn(H2O)6]2+ into [Zn(H2O)4LAA], thus reducing the coordinated H2O molecules and further suppressing side reactions. With this synergy effect, the Zn/Zn symmetric battery with the ZSO + LAA electrolyte can deliver a cycle life of 1200 h under 1 mA cm-2, and the Zn/Ti battery also presents an ultrahigh Coulombic efficiency of 99.16% under 1 mA cm-2, greatly superior to the batteries with the ZSO electrolyte. Additionally, the effectiveness of the LAA additive can be further verified in the Zn/MnO2 full battery and pouch cell.

Enhancing the Luminescence of Eu(III) Complexes with the Ruthenocene Organometallic Unit as Ancillary Ligand.

Five novel Eu(III)-β-diketonate complexes containing ruthenocene ancillary ligands (1,1'-bis(diphenylphosphoryl)ruthenocene─RcBPO) were synthesized and characterized. The coordination compounds presented the general formula [Eu(β-dik)3(RcBPO)], where β-dik stands for 2-thenoyltrifluoroacetonate (tta), 3-benzoyl-1,1,1-trifluoroacetone (btf), 2-dibenzoylmethanate (dbm), 2-acetyl-1,3-indandionate (aind), and 2-benzoyl-1,3-indandionate (bind), and RcBPO stands for 1,1'-bis(diphenylphosphoryl)ruthenocene. The [Eu(aind)3(RcBPO)] complex crystallizes in a monoclinic Cc non-centrosymmetric space group with the europium site environment, assuming a bicapped trigonal prism coordination polyhedron with the symmetry point group close to C2v. Photoluminescent properties for the solid-state samples were described in terms of excitation, emission, lifetime decay curves, and intrinsic and overall quantum yields. The replacement of the two coordinated H2O molecules by the RcBPO ancillary ligand leads to great enhancements of the overall quantum yields (QEuL), with the minimum increment by a factor of 5 for the case of [Eu(btf)3(RcBPO)] and the maximum enhancement of 270 times for the case of the [Eu(dbm)3(RcBPO)] complex. In addition, theoretical calculations were carried out to model the spectroscopic properties of the investigated compounds. To obtain theoretical Judd-Ofelt parameters (Ωλ, λ = 2, 4, and 6) and intramolecular energy transfer rates, the JOYSpectra web platform was employed using the structure obtained from density functional theory calculations. Hence, a rate equation model provided theoretical overall quantum yields, which are in great agreement with measured data.

Dual-ligand lanthanide metal–organic framework for ratiometric fluorescence detection of the anthrax biomarker dipicolinic acid

Dipicolinic acid (DPA) is a unique biomarker of Bacillus anthracis. Development of a simple, fast, sensitive and timely DPA detection method is of great importance and interest for preventing mass disease outbreaks and treatment of anthrax. In this work, a novel lanthanide-doped fluorescence probe was constructed by coordination of Eu3+ with bifunctional UiO-66-(COOH)2-NH2 MOFs materials for efficient monitoring DPA. UiO-66-(COOH)2-NH2 MOFs were prepared using Zr4+ as a metal node, 1,2,4,5-benzenetetracarboxylic acid (H4BTC) and 2-aminoterephthalic acid (NH2-BDC) as bridging ligand through a simple one-pot synthesis method. By virtue their abundant carboxyl groups, UiO-66-(COOH)2-NH2 can readily grasp Eu3+ to form UiO-66-(COOH)2-NH2/Eu with coordinated water molecules at Eu sites. Upon interaction with DPA molecules, the coordinated H2O molecules were replaced by DPA molecules which transfer energy to Eu3+ in UiO-66-(COOH)2-NH2/Eu and sensitize Eu3+ luminescence. Meanwhile, DPA has a characteristic absorption band at 270 nm, which overlapped with the excitation spectrum of NH2-BDC, allowing the fluorescence of UiO-66-(COOH)2-NH2/Eu at 453 nm to be greatly quenched by DPA through inner filter effect (IFE). Therefore, the rationally designed UiO-66-(COOH)2-NH2/Eu complex not only exhibits strong hydrophilicity and high dispersion, but also serves as ratiometric fluorescence sensing platform for monitoring DPA concentration. This sensing platform showed a satisfactory linear relationship from 0.2 μM to 40 μM with a limit of detection of 25.0 nM and a noticeable fluorescence color change from blue to red, holding a great promise in practical applications.

A new 3D supramolecular Zn(II) compound: Crystal structure and important role in treatment of pulpitis

An innovative thermostable 2-D layered Zn(II) compound, chemical terms are written as [Zn(3-pysa)2(H2O)2]n (1, 3-Hpysa = 3-pyridinesulfonic acid), has been generated from the solvothermal reactions of 3-Hpysa and Zn(NO3)2·6H2O. Its single crystal analysis was implemented via the single crystal X-ray diffraction analysis together with the powder X-ray diffraction, elemental analysis and thermogravimetric analysis. The crystal framework is of monoclinic P21/n space group and its crystal cell figures: a = 7.7499(5), b = 10.9923(6), c = 8.3430(5) Å, α = 90, β = 96.924(6), γ = 90°, V = 705.55(7) Å3, Z = 4. The 2D layers were finally combined to a 3-D supramolecular conformation through intermolecular H-bonds existing between coordinated H2O molecules and sulfonate oxygen atoms from adjacent layer. Its practical role in pulpitis treatment was estimated and the relevant mechanism was studied in the meantime.

Stable Lanthanide Metal-Organic Frameworks with Ratiometric Fluorescence Sensing for Amino Acids and Tunable Proton Conduction and Magnetic Properties.

Four new isostructural lanthanide metal-organic frameworks (MOFs), namely {[Ln(DMTP-DC)1.5(H2O)3]·DMF}n [H2DMTP-DC = 2',5'-dimethoxytriphenyl-4,4″-dicarboxylic acid; LnIII = EuIII (1), GdIII (2), TbIII (3), and DyIII (4)], have been synthesized and characterized. Single-crystal structure analysis reveals that 1-4 are three-dimensional Ln-MOFs with rich H-bonding of coordinated H2O molecules in the network channels. The X-ray diffraction patterns indicate that Ln-MOF 1 displays good stabilities in organic solvents and aqueous solutions with distinct pH values. Both 1 and 3 show characteristic emission of LnIII ions. Ln-MOF 1 can be used as a ratiometric fluorescence sensor for arginine and lysine in aqueous solution, and the detection limits are 24.38 μM for arginine and 9.31 μM for lysine. All 1-4 show proton conductivity related to relative humidity (RH) and temperature, and the maximum conductivity values of 1-4 at 55 °C and 100% RH are 9.94 × 10-5, 1.62 × 10-4, 1.71 × 10-4, and 2.67 × 10-4 S·cm-1, respectively. The value of σ increases with the decrease in ionic radius, indicating that the radius of the LnIII ions can regulate the proton conductivity of these MOFs. Additionally, 2 exhibits a significant magnetocaloric effect (MCE) with a magnetic entropy change (-ΔSm) of 18.86 J kg-1 K-1 for ΔH = 7 T at 2 K, and 4 shows weak field-induced slow relaxation of magnetization. The coexistence of good fluorescence sensing capability, attractive proton conductivity, and relatively large MCE in Ln-MOFs is rare, and thus, 1-4 are potentially multifunctional MOF materials.

Water Molecules in Channels of Natural Emeralds from Dayakou (China) and Colombia: Spectroscopic, Chemical and Crystal Structural Investigations

H2O molecules in emerald channels have been extensively discussed over the past half century. Recent studies paid attention to their classification and coordination, but have mostly focused on the type related to Na+. There are few works on the other types, and the related infrared (IR) absorption bands are rather controversial. This paper investigated natural emeralds from China and Colombia by means of micro-Fourier transform infrared (μ-FTIR) spectroscopy, micro-confocal Raman spectroscopy, and laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). The results suggested that doubly (IId) and singly (IIs) coordinated H2O molecules were incorporated in natural emerald channels. Type IId H2O predominated in those emeralds with relatively low alkali content. As the alkali content increased, the proportion of type IIs H2O rose, stemming from the decrease of the H2OII/Na+ apfu ratio. Moreover, IR bands of H2O corresponding to Li+ and Cs+ were tentatively ascribed here. IR bands for D2O and HDO in Colombian sample were observed in the range of 2600–2850 cm−1 and preliminarily assigned, which might be a potential tool for emerald origin determination. Our work expanded the existing classification of water molecules in emerald channels and redefined the controversial IR absorption bands.

Whither Second-Sphere Coordination?

Whither Second-Sphere Coordination?

CO2‐Induced 2D Ni‐BDC Metal–Organic Frameworks with Enhanced Photocatalytic CO2 Reduction Activity

AbstractThe rational design of 2D metal–organic framework (MOF) nanosheets with high active exposed surfaces and ultrathin thickness is a critical issue for CO2 reduction. How to fabricate 2D MOFs and simultaneously fulfill the strong adsorption and activation of CO2 molecules is a great challenge. Here, it is reported that CO2 molecules can help to fabricate single‐layer [Ni3(OH)2(1,4‐BDC)2‐(H2O)4]·2H2O, BDC = 1,4‐benzenedicarboxylate, (Ni‐BDC) MOF nanosheets with large sizes and uniform thickness by exchanging with the coordinated H2O molecules at Ni sites and further orientated chemically adsorption on it. CO2 molecules can not only help break the interlayer hydrogen bond of bulk materials realizing the successful transformation from 3D to 2D, but also contribute to expose the (200) planes with highly active in photocatalytic CO2‐to‐CO conversion, and a high production rate of 104 mmol g−1 h−1 and a high Faraday efficiency of 96.8% can be obtained. This strategy provides a novel prototypical model based on the strong interaction between metal active centers and reactive molecules to obtain 2D MOFs with high quality and activity.

Simultaneous quantitative recognition of all purines including N6-methyladenine via the host-guest interactions on a Mn-MOF

Simultaneous quantitative recognition of all purines including N6-methyladenine via the host-guest interactions on a Mn-MOF

The kinetics and mechanism of the ligand substitution reaction of aquapentacyanoruthenate(II) with d-penicillamine in aqueous medium

The kinetics of the formation of the light orange–coloured complex [Ru(CN)5D-PA]3− are studied spectrophotometrically through substitution of a coordinated H2O molecule in aquapentacyanoruthenate(II) [Ru(CN)5OH2]3− by interaction with D-penicillamine [D-PA] in aqueous medium at 490 nm (λmax of [Ru(CN)5D-PA]3−). The reaction is monitored under pseudo-first-order conditions, taking [D-PA] in excess over [Ru(CN)5OH23−]. The effects of various reaction parameters on the rate of the reaction are investigated. Experimental observations reveal that the variation in [D-PA] obeyed the first-order rate law while it is found to be invariant with [Ru(CN)5OH23−] in the whole experimental range. With ionic strength variation, as the reaction advances a decrease in the reaction rate is noticed. The product stoichiometry is assigned as 1:1. The ease of substitution at an H2O molecule in [Ru(CN)5OH23−] is considered on the basis of the electronic effect generated through interactions of the M–OH2 bond. A provisional mechanism based on the calculated results is proposed based on the slowest step of the reaction.

A Facile Electrosynthesis of Terephthalate (tp)‐Based Metal‐Organic Framework, Ni3(OH)2(H2O)2(tp)2 with Superior Catalytic Activity for Hydrogen Evolution Reaction

Utilizing a facile one‐step electrodeposition method, several terephthalate (tp)‐based MOFs, M3(OH)2(H2O)2(tp)2 (M = Ni, Co or Fe) have been synthesized on Ni foam (NF) or carbon cloth (CC). Among the MOFs, Ni‐MOF/NF shows porous nanosheet arrays on NF and exhibits extraordinary hydrogen evolution reaction (HER) catalytic activity with an overpotential (η10) of 60 mV to reach a current density of –10 mA cm–2, which is superior to Co‐MOF/NF (η10 = 184 mV) and Fe‐MOF/NF (η10 = 203 mV), and even comparable to Pt/C (η10 = 23 mV), indicating the HER performance is associated with the species of metal ions and the morphology. In addition, it is primarily investigated the formation mechanism of Ni‐MOF nanosheet arrays on Ni foam. Furthermore, Ni‐MOF/NF can endure 50 h‐electrolysis test at –20 mA cm–2 in alkaline condition. Density functional theory (DFT) calculations identify the active site of Ni3(OH)2 (H2O)2(tp)2 for HER is the O‐site from the coordinated ‐OH group (ΔGH=–0.40 eV) rather than the O‐site from the coordinated H2O molecule (ΔGH = –1.75 eV).

An anionic cadmium-organic framework with an uncommon 3,3,4,8-c network for efficient organic dye separation

A novel anionic metal–organic framework (MOF), {[Cd5(L)4·Na2·(H2O)]·2(CH3)2NH2·3DMF} (LYU-2, Linyi University) (H5L = 2,5-bis(3′,5′-dicarboylphenyl)-benzoic acid), has been solvothermally synthesized and characterized. LYU-2 contains microporous channels with a complicated 3D tetranodal 3,3,4,8-c network, uncoordinated carboxylate groups and coordinated H2O molecules, exhibiting excellent selective adsorption and separation of small cationic dyes through an ion-exchange process in aqueous solution. According to UV/Vis spectroscopy analysis of LYU-2, methylene blue (MB+) and crystal violet (CV+) can be rapidly adsorbed, whereas larger rhodamine B (RB+), anionic methyl orange (MO−), and neutral sudan II (SD0) can hardly be adsorbed. The results imply that the adsorption of dye molecules in LYU-2 displays not only a charge effect, but also a size- and shape-exclusive effect. Furthermore, the adsorbed MB+ can be gradually released in a NaCl-containing aqueous solution.

A Bilayer Structure Composed of Mg|Co-MnO2 Deposited on a Co(OH)2 Film to Realize Selective Oxygen Evolution from Chloride-Containing Water.

A fluorine-doped tin oxide-coated glass electrode modified with a bilayer film of underlying α-Co(OH)2 and overlying Mg-intercalated and Co-doped δ-type (layered) MnO2 (Mg|Co-MnO2) preferentially yielded oxygen with a Faradaic efficiency as high as 79% in the presence of chloride ions at high concentration (0.5 M). This noble metal-free electrode was fabricated by cathodic electrolysis of aqueous Co(NO3)2 followed by anodic electrolysis of a mixture of Mn2+, Co2+, and cetyltrimethylammonium (CTA+) ions in water. The CTA+ ions accommodated in the interlayer spaces of Co-doped δ-MnO2 were replaced with Mg2+ by ion exchange. The upper Mg|Co-MnO2 could effectively block the permeation of Cl- ions and allow only H2O and O2, while the under α-Co(OH)2 acted as an oxidation catalyst for the H2O penetrated through the upper coating. Thus, the oxygen evolution reaction (OER) was preferred to the chlorine evolution reaction (CER). In artificial seawater (pH 8.3), the blocking effect against Cl- decreased because of ion exchange of the intercalated Mg2+ ions with Na+ in solution, but the OER efficiency still remained at 57%, much higher than that (28%) without the upper Mg|Co-MnO2. This demonstrates that the interlayer spaces between MnO2 layers acted as pathways for H2O molecules to reach the active sites of the underlying Co(OH)2. Density functional theory (DFT) calculations revealed that the most stable structure of hydrated Mg2+ ion, in which a part of coordinated H2O molecules is hydrolyzed, has less affinity toward Cl- ion than that of hydrated Na+ ion.

A giant hybrid organic-inorganic octahedron from a narrow rim carboxylate calixarene.

Here we discovered an unprecedented giant octahedral coordination compound bearing 16 Zn2+, 12 Na+, 8 O2-, 4 OH-, 13 H2O and 6 L4- ligands [L4- = fully deprotonated tetra(carboxymethoxy)calix[4]arene]. Its structure was elucidated by single-crystal X-ray diffraction, wavelength-dispersive X-ray spectroscopy and MALDI-TOF mass spectrometry. This compound, Zn8Na6L6⊃Zn8Na6O8(OH)4(H2O)13 (external⊃internal), has eight tetrahedral zinc ions forming the coordination vertices of an outermost cube where carboxylate groups from the sodium calixarenes are anchored. Its core consists of eight Zn2+, six Na+, eight O2-, and four OH- distributed over three layers, besides thirteen coordinated H2O molecules.

RETRACTED: Water-stable Ln-exclusive metal-organic framework for highly selective sensing of Fe3+ ions

Abstract The design and synthesis of high stability lanthanide complexes with ion detection has been widely attentions and certain challenges. In this work, we successfully synthesized and designed a series of 2D Ln-MOFs ([Ln2(L1)2(H2O)4]·2H2O, Ln = Tb (MOF-1), Eu (MOF-3); [Tb2(L1)2(DMF)(H2O)] (MOF-2)). Structural analysis suggests that every Ln(III) ion is surrounded by six O ions from four L1 ligands, and two oxygen atoms from water molecules of MOF-1 and MOF-3. For MOF-2, the asymmetric unit consists of two different coordination of Tb(III) ions, two L1 ligands, one coordinated dimethylformamide (DMF) and one coordinated H2O molecule. The eight-coordinated Tb1 is surrounded by five O ions/atoms and two μ2-O- ions from four L1 ligands; and one O atom from one coordinated H2O molecule, The seven-coordinated Tb2 is surrounded by four O ions/atoms and two μ2-O- ions from four L1 ligands and one O atom from one coordinated DMF molecule. The results of various metal ions sensing show that those three Ln-MOFs have high efficiency, sensitivity and specificity in the recognition of Fe3+ ions in aqueous solution. Further tests show that the minimum detection concentration of Fe3+ ions in an aqueous solution of the above three cases of Ln-MOFs is 10−6 M, and the interference of other ions in the solution can be effectively avoided.