Post‐Synthetic Reversible Incorporation of Organic Linkers into Porous Metal–Organic Frameworks through Single‐Crystal‐to‐Single‐Crystal Transformations and Modification of Gas‐Sorption Properties

The porous metal–organic framework (MOF) {[Zn₂(TCPBDA)(H₂O)₂]?30 DMF?6 H₂O}_n ( SNU‐30 ; DMF=N,N‐dimethylformamide) has been prepared by the solvothermal reaction of N,N,N′,N′‐tetrakis(4‐carboxyphenyl)biphenyl‐4,4′‐diamine (H₄TCPBDA) and Zn(NO₃)₂?6 H₂O in DMF/tBuOH. The post‐synthetic modification of SNU‐30 by the insertion of 3,6‐di(4‐pyridyl)‐1,2,4,5‐tetrazine (bpta) affords single‐crystalline {[Zn₂(TCPBDA)(bpta)]?23 DMF?4 H₂O}_n ( SNU‐31 SC ), in which channels are divided by the bpta linkers. Interestingly, unlike its pristine form, the bridging bpta ligand in the MOF is bent due to steric constraints. SNU‐31 can be also prepared through a one‐pot solvothermal synthesis from Zn^II, TCPBDA^4?, and bpta. The bpta linker can be liberated from this MOF by immersion in N,N‐diethylformamide (DEF) to afford the single‐crystalline SNU‐30 SC , which is structurally similar to SNU‐30 . This phenomenon of reversible insertion and removal of the bridging ligand while preserving the single crystallinity is unprecedented in MOFs. Desolvated solid SNU‐30′ adsorbs N₂, O₂, H₂, CO₂, and CH₄ gases, whereas desolvated SNU‐31′ exhibits selective adsorption of CO₂ over N₂, O₂, H₂, and CH₄, thus demonstrating that the gas adsorption properties of MOF can be modified by post‐synthetic insertion/removal of a bridging ligand.     

Assembly of 3D Coordination Polymers from 2D Sheets by [2+2] Cycloaddition Reaction

The synthesis of three 2D interdigitated Zn^II coordination polymers (CPs), by using three monotopic ligands containing C?C bonds, is reported. Among these, two CPs with 4spy (4‐styryl pyridine) and 2F‐4spy (a 2′‐fluoro derivative of 4spy) ligands showed quantitative formation of cyclobutane rings, thus demonstrating a unique synthetic procedure to synthesize metal–organic frameworks (MOFs) by using this photochemical reaction. Interestingly, these compounds can also be synthesized by mechanochemical grinding procedures by using Zn(OAc)₂. In contrast, Zn(NO₃)₂ did not yield the required product, unlike in the solution route. In addition, compounds with 4vpy (4‐vinylpyridine), 4spy and 2F‐4spy ligands created different units in the CPs; 4vpy and 2F‐4spy furnished paddle wheel units, whereas 4spy yielded tetrahedral Zn^II repeating units. Furthermore, the change in coordination geometry manifests in the photoluminescence properties, attributed to the difference in charge‐transfer and ligand‐centered fluorescent phenomenon.     

A Water‐Stable Terbium(III)–Organic Framework as a Chemosensor for Inorganic Ions,Nitro‐Containing Compounds and Antibiotics in Aqueous Solutions

Effective detection of organic/inorganic pollutants, such as antibiotics, nitro‐compounds, excessive Fe³⁺ and MnO₄^?, is crucial for human health and environmental protection. Here, a new terbium(III)–organic framework, namely [Tb(TATAB)(H₂O)]?2H₂O ( Tb‐MOF , H₃TATAB=4,4′,4′′‐s‐triazine‐1,3,5‐triyltri‐m‐aminobenzoic acid), was assembled and characterized. The Tb‐MOF exhibits a water‐stable 3D bnn framework. Due to the existence of competitive absorption, Tb‐MOF has a high selectivity for detecting Fe³⁺, MnO₄^?, 4‐nirophenol and nitroimidazole (ronidazole, metronidazole, dimetridazole, ornidazole) in aqueous through luminescent quenching. The results suggest that Tb‐MOF is a simple and reliable reagent with multiple sensor responses in practical applications. To the best of our knowledge, this work represents the first Tb^III‐based MOF as an efficient fluorescent sensor for detecting metal ions, inorganic anions, nitro‐compounds, and antibiotics simultaneously.     

A 2D Metal‐Organic Framework Based on 9‐(Pyridin‐4‐yl)‐9H‐carbazole‐3,6‐dicarboxylic Acid: Synthesis,Structure and Properties

A metal‐organic framework (MOF ) formulated as [Cd₂(μ₃‐L)₂(DMF )₄]•H₂O ( CdL ) [H₂L =9‐(pyridin‐4‐yl)‐ 9H ‐carbazole‐3,6‐dicarboxylic acid, DMF =N ,N ‐dimethylformamide] was synthesized under solvothermal condition. Crystal structural analysis reveals that CdL features the layered 2D framework with L^{2 −} ligands as 3‐connected nodes. The compound CdL emits blue‐violet light with the narrow emission peak and the emission maximum at 414 nm upon excitation at the maximum excitation wavelength of 340 nm. The compound CdL has a similar emission spectrum curve to the free H₂L ligand that indicates the emission of compound CdL should be originated from the coordinated L^{2 −} ligands.     

Controllable Syntheses of Porous Metal–Organic Frameworks: Encapsulation of LnIII Cations for Tunable Luminescence and Small Drug Molecules for Efficient Delivery

Two porous metal–organic frameworks (MOFs), [Zn₃(L)(H₂O)₂] ? 3 DMF ? 7 H₂O ( MOF‐1 ) and [(CH₃)₂NH₂]₆[Ni₃(L)₂(H₂O)₆] ? 3 DMF ? 15 H₂O ( MOF‐2 ), were synthesized solvothermally (H₆L=1,2,3,4,5,6‐hexakis(3‐carboxyphenyloxymethylene)benzene). In MOF ‐ 1 , neighboring Zn^II trimers are linked by the backbones of L ligands to form a fascinating 3D six‐connected framework with the point symbol (4¹².6³) (4¹².6³). In MOF‐2 , eight L ligands bridge six Ni^II atoms to generate a rhombic‐dodecahedral [Ni₆L₈] cage. Each cage is surrounded by eight adjacent ones through sharing of carboxylate groups to yield an unusual 3D porous framework. Encapsulation of Ln^III cations for tunable luminescence and small drug molecules for efficient delivery were investigated in detail for MOF‐1 .     

A Robust Porous Metal–Organic Framework with a New Topology That Demonstrates Pronounced Porosity and High‐Efficiency Sorption/Selectivity Properties of Small Molecules

A robust porous metal–organic framework (MOF), [Co₃(ndc)(HCOO)₃(μ₃‐OH)(H₂O)]_n ( 1 ) (H₂ndc=5‐(4‐pyridyl)‐isophthalic acid), was synthesized with pronounced porosity. MOF 1 contained two different types of nanotubular channels, which exhibited a new topology with the Schlafli symbol of {4².6⁵.8³}{4².6}. MOF 1 showed high‐efficiency for the selective sorption of small molecules, including the energy‐correlated gases of H₂, CH₄, and CO₂, and environment‐correlated steams of alcohols, acetone, and pyridine. Gas‐sorption experiments indicated that MOF 1 exhibited not only a high CO₂‐uptake (25.1 wt % at 273 K/1 bar) but also the impressive selective sorption of CO₂ over N₂ and CH₄. High H₂‐uptake (2.04 wt % at 77 K/1 bar) was also observed. Moreover, systematic studies on the sorption of steams of organic molecules displayed excellent capacity for the sorption of the homologous series of alcohols (C₁–C₅), acetone, pyridine, as well as water.     

Structural analysis of interpenetrated methyl‐modified MOF‐5 and its gas‐adsorption properties

The first example of an interpenetrated methyl‐modified MOF‐5 with the formula Zn₄O(DMBDC)₃(DMF)₂, where DMBDC^2? is 2,5‐dimethylbenzene‐1,4‐dicarboxylate and DMF is N,N‐dimethylformamide (henceforth denoted as Me₂MOF‐5‐int ), namely, poly[tris(μ₄‐2,5‐dimethylbenzene‐1,4‐dicarboxylato)bis(N,N‐dimethylformamide)‐μ₄‐oxido‐tetrazinc(II)], [Zn₄(C₁₀H₈O₄)₃O(C₃H₇NO)₂]_n, has been obtained from a solvothermal synthesis of 2,5‐dimethylbenzene‐1,4‐dicarboxylic acid and Zn(NO₃)₂·6H₂O in DMF. A systematic study revealed that the choice of solvent is of critical importance for the synthesis of phase‐pure Me₂MOF‐5‐int , which was thoroughly characterized by single‐crystal and powder X‐ray diffraction (PXRD), as well as by gas‐adsorption analyses. The Brunauer–Emmett–Teller surface area of Me₂MOF‐5‐int (660 m² g^?1), determined by N₂ adsorption, is much lower than that of nonpenetrated Me₂MOF‐5 (2420 m² g^?1). However, Me₂MOF‐5‐int displays an H₂ uptake capacity of 1.26 wt% at 77 K and 1.0 bar, which is comparable to that of non‐interpenetrated Me₂MOF‐5 (1.51 wt%).     

Tetrazine Chromophore‐Based Metal–Organic Frameworks with Unusual Configurations: Synthetic,Structural, Theoretical,Fluorescent, and Nonlinear Optical Studies

Three unusual three‐dimensional (3D) tetrazine chromophore‐based metal–organic frameworks (MOFs) {(Et₄N)[WS₄Cu₃(CN)₂(4,4′‐pytz)_0.5]}_n ( 1 ), {[MoS₄Cu₄(CN)₂(4,4′‐pytz)₂] ? CH₂Cl₂}_n ( 2 ), and {[WS₄Cu₃(4,4′‐pytz)₃] ? [N(CN)₂]}_n ( 3 ; 4,4′‐pytz=3,6‐bis(4‐pyridyl)tetrazine) have been synthesized and characterized by using FTIR and UV/Vis spectroscopy, elemental analysis, powder X‐ray diffraction, gel permeation chromatography, steady‐state fluorescence, and thermogravimetric analysis; their identities were confirmed by single‐crystal X‐ray diffraction studies. MOF 1 possesses the first five‐connected M/S/Cu (M=Mo, W) framework with an unusual 3D (4⁴?6⁶) topology constructed from T‐shaped [WS₄Cu₃]⁺ clusters as nodes and single CN^?/4,4′‐pytz bridges as linkers. MOF 2 features a novel 3D MOF structure with (4²⁰?6⁸) topology, in which the bridging 4,4′‐pytz ligands exhibit unique distorted arch structures. MOF 3 displays the first 3D MOF structure based on flywheel‐shaped [WS₄Cu₃]⁺ clusters with a non‐interpenetrating honeycomb‐like framework and a heavily distorted “ACS” topology. Steady‐state fluorescence studies of 1 – 3 reveal significant fluorescence emissions. The nonlinear optical (NLO) properties of 1 – 3 were investigated by using a Z‐scan technique with 5 ns pulses at λ=532 nm. The Z‐scan experimental results show that the π‐delocalizable tetrazine‐based 4,4′‐pytz ligands contribute to the strong third‐order NLO properties exhibited by 1 – 3 . Time‐dependent density functional theory studies afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.     

Enhanced CO2 Adsorption Affinity in a NbO‐type MOF Constructed from a Low‐Cost Diisophthalate Ligand with a Piperazine‐Ring Bridge

A metal–organic framework (NPC‐6) with an NbO topology based on a piperazine ring‐bridged diisophthalate ligand was synthesized and characterized. The incorporated piperazine group leads to an enhanced adsorption affinity for CO₂ in NPC‐6, in which the CO₂ uptake is 4.83 mmol g^?1 at 293 K and 1 bar, ranking among the top values of CO₂ uptake on MOF materials. At 0.15 bar and 293 K, the NPC‐6 adsorbs 1.07 mmol g^?1 of CO₂, which is about 55.1 % higher than that of the analogue MOF NOTT‐101 under the same conditions. The enhanced CO₂ uptake combined with comparable uptakes for CH₄ and N₂ leads to much higher selectivities for CO₂/CH₄ and CO₂/N₂ gas mixtures on NPC‐6 than on NOTT‐101. Furthermore, an N‐alkylation is used in the synthesis of the PDIA ligand, leading to a much lower cost compared with that in the synthesis of ligands in the NOTT series, as the former does not require a palladium‐based catalyst and borate esters. Thus, we conclude that NPC‐6 is a promising candidate for CO₂ capture applications.     

A Bifunctional Luminescent Metal–Organic Framework for the Sensing of Paraquat and Fe3+ Ions in Water

The hydrothermal reaction of Zn²⁺ ions with a mixture of two ligands, Hcptpy and H₃btc (Hcptpy=4‐(4‐carboxyphenyl)‐2,2′:4′,4′′‐terpyridine; H₃btc=1,3,5‐benzenetricarboxylic acid), led to the formation of a 3D metal–organic framework (MOF) with 1D channels, [Zn₂(cptpy)(btc)(H₂O)]_n ( 1 ), which was structurally characterized by using single‐crystal X‐ray diffraction (SXRD). In MOF 1 , two independent Zn²⁺ ions were interconnected by btc^3? ligands to form a 1D chain, whilst adjacent Zn²⁺ ions were alternately bridged by cptpy^? ligands to generate a 2D sheet, which was further linked by 1D chains to form a 3D framework with a new (3,3,4,4)‐connected topology. Furthermore, compound 1 also exhibited excellent stability towards air and water and, more importantly, luminescence experiments indicated that it could serve as a probe for the sensitive detection of paraquat (PAQ) and Fe³⁺ ions in aqueous solution.     

A fourfold interpenetrating cadmium(II) metal–organic framework based on 2,4,6‐tris(pyridin‐4‐yl)‐1,3,5‐triazine with reversible photochromic properties

2,4,6‐Tris(pyridin‐4‐yl)‐1,3,5‐triazine (tpt), as an organic molecule with an electron‐deficient nature, has attracted considerable interest because of its photoinduced electron transfer from neutral organic molecules to form stable anionic radicals. This makes it an excellent candidate as an organic linker in the construction of photochromic complexes. Such a photochromic three‐dimensional (3D) metal–organic framework (MOF) has been prepared using this ligand. Crystallization of tpt with Cd(NO₃)₂·4H₂O in an N,N‐dimethylacetamide–methanol mixed‐solvent system under solvothermal conditions afforded the 3D MOF poly[[bis(nitrato‐κ²O,O′)cadmium(II)]‐μ₃‐2,4,6‐tris(pyridin‐4‐yl)‐1,3,5‐triazine‐κ³N²:N⁴:N⁶], [Cd(NO₃)₂(C₁₈H₁₂N₆)]_n, which was characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis and single‐crystal X‐ray diffraction. The X‐ray diffraction crystal structure analysis reveals that the asymmetric unit contains one independent Cd^II cation, one tpt ligand and two coordinated NO₃^? anions. The Cd^II cations are connected by tpt ligands to generate a 3D framework. The single framework leaves voids that are filled by mutual interpenetration of three independent equivalent frameworks in a fourfold interpenetrating architecture. The compound shows a good thermal stability and exhibits a reversible photochromic behaviour, which may originate from the photoinduced electron‐transfer generation of radicals in the tpt ligand.     

A novel two‐dimensional cadmium(II) complex: poly[diaquatris(μ4‐cyclohexane‐1,4‐dicarboxylato)bis[2‐(pyridin‐4‐yl)‐1H‐benzimidazole]tricadmium(II)

The title compound, [Cd₃(C₈H₁₀O₄)₃(C₁₂H₉N₃)₂(H₂O)₂]_n or [Cd₃(chdc)₃(4‐PyBIm)₂(H₂O)₂]_n, was synthesized hydrothermally from the reaction of Cd(CH₃COO)₂·2H₂O with 2‐(pyridin‐4‐yl)‐1H‐benzimidazole (4‐PyBIm) and cyclohexane‐1,4‐dicarboxylic acid (1,4‐chdcH₂). The asymmetric unit consists of one and a half Cd^II cations, one 4‐PyBIm ligand, one and a half 1,4‐chdc²⁻ ligands and one coordinated water molecule. The central Cd^II cation, located on an inversion centre, is coordinated by six carboxylate O atoms from six 1,4‐chdc²⁻ ligands to complete an elongated octahedral coordination geometry. The two terminal rotationally symmetric Cd^II cations each exhibits a distorted pentagonal–bipyramidal geometry, coordinated by one N atom from 4‐PyBIm, five O atoms from three 1,4‐chdc²⁻ ligands and one O atom from an aqua ligand. The 1,4‐chdc²⁻ ligands possess two conformations, i.e.e,e‐trans‐chdc²⁻ and e,a‐cis‐chdc²⁻. The cis‐1,4‐chdc²⁻ ligands bridge the Cd^II cations to form a trinuclear {Cd₃}‐based chain along the b axis, while the trans‐1,4‐chdc²⁻ ligands further link adjacent one‐dimensional chains to construct an interesting two‐dimensional network.     

Adsorption behaviour of a CdII–triazole MOF for butan‐2‐one in a single‐crystal‐to‐single‐crystal (SCSC) fashion: the role of hydrogen bonding and C—H…π interactions

The adsorption behaviour of the Cd^II–MOF {[Cd(L)₂(ClO₄)₂]·H₂O ( 1 ), where L is 4‐amino‐3,5‐bis[3‐(pyridin‐4‐yl)phenyl]‐1,2,4‐triazole, for butan‐2‐one was investigated in a single‐crystal‐to‐single‐crystal (SCSC) fashion. A new host–guest system that encapsulated butan‐2‐one molecules, namely poly[[bis{μ₃‐4‐amino‐3,5‐bis[3‐(pyridin‐4‐yl)phenyl]‐1,2,4‐triazole}cadmium(II)] bis(perchlorate) butanone sesquisolvate], {[Cd(C₂₄H₁₈N₆)₂](ClO₄)₂·1.5C₄H₈O}_n, denoted C₄H₈O@Cd‐MOF ( 2 ), was obtained via an SCSC transformation. MOF 2 crystallizes in the tetragonal space group P4₃2₁2. The specific binding sites for butan‐2‐one in the host were determined by single‐crystal X‐ray diffraction studies. N—H…O and C—H…O hydrogen‐bonding interactions and C—H…π interactions between the framework, ClO₄^? anions and guest molecules co‐operatively bind 1.5 butan‐2‐one molecules within the channels. The adsorption behaviour was further evidenced by ¹H NMR, IR, TGA and powder X‐ray diffraction experiments, which are consistent with the single‐crystal X‐ray analysis. A ¹H NMR experiment demonstrates that the supramolecular interactions between the framework, ClO₄^? anions and guest molecules in MOF 2 lead to a high butan‐2‐one uptake in the channel.     

Characterization and gas adsorption of a novel three‐dimensional metal–organic framework (MOF) generated from a new polydentate fluorene‐bridged ligand

A polydentate ligand bridged by a fluorene group, namely 9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene (L), has been prepared under solvothermal conditions in acetonitrile. Crystals of the three‐dimensional metal–organic framework (MOF) poly[[[μ₃‐9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene‐κ³N:N′:O]bis(methanol‐κO)(μ‐sulfato‐κ²O:O′)nickel(II)] methanol disolvate], {[Ni(SO₄)(C₂₇H₂₄N₂O₂)(CH₃OH)]·2CH₃OH}_n, (I), were obtained by the solvothermal reaction of L and NiSO₄ in methanol. The ligand L forms a two‐dimensional network in the crystallographic bc plane via two groups of O—H…N hydrogen bonds and neighbouring two‐dimensional planes are completely parallel and stack to form a three‐dimensional structure. In (I), the Ni^II ions are linked by sulfate ions through Ni—O bonds to form inorganic chains and these Ni‐containing chains are linked into a three‐dimensional framework via Ni—O and Ni—N bonds involving the polydentate ligand L. With one of the hydroxy groups of L coordinating to the Ni^II atom, the torsion angle of the hydroxyethyl group changes from that of the uncoordinated molecule. In addition, the adsorption properties of (I) with carbon dioxide were investigated.     

A Step‐by‐Step Assembly of a 3D Coordination Polymer in the Solid‐State by Desolvation and [2+2] Cycloaddition Reactions

Two solid‐state structural transformations that occur in a stepwise and a controlled manner are described. A combination of desolvation and cycloaddition reactions has been employed to synthesise a 3D coordination polymer (CP) from 1D CP [Cd(bdc)(4‐spy)₂(H₂O)]?2 H₂O?2 DMF (bdc=1,4‐benzenedicarboxylate, 4‐spy=4‐styrylpyridine) presumably via a 2D layered structure, [Cd₂(bdc)₂(4‐spy)₄]. In the absence of single crystals to follow the course of the photocycloaddition reaction, thermogravimetry, XAFS and NOESY NMR experiments were used to propose the formation of layered and pillared layered structures. Further, the present strategy enables us to synthesise new multidimensional architectures that are otherwise inaccessible by the self‐assembly process.     

Construction of Two High‐Nuclear 3d‐4d Heterometallic Cluster Organic Frameworks by Introducing a Bifunctional Tripodal Alcohol as a Structure‐Directing Agent

Two unique heterometallic cluster organic frameworks, [Cd₄Mn^III₄Mn^II₆(Tri)₄(CH₃COO)₁₄(μ₄‐O)₂(μ₃‐O)₂(H₂O)₂] Cd(H₂O)₂?9 H₂O ( 1 ) and Cu[Cd₅Cu₆(Tri)₄(CH₃COO)₉(H₂O)₄]₂(CH₃COO)₃?24 H₂O ( 2 ) (H₃Tri=2‐(hydroxymethyl)‐2‐(pyridine‐4‐yl)‐1,3‐propanediol), have been successfully prepared by employing a bifunctional tripodal alcohol ligand as a structure‐directing agent. Crystal structure analyses reveal that 1 represents a rare example of frameworks constructed from Cd?Mn heterometallic chains, and 2 is the first heterometallic MOF based on highest‐nuclear Cd?Cu heterometallic cluster building blocks. Furthermore, the magnetic properties and gas adsorption abilities of 1 and 2 were systematically studied.     

A Cationic MOF with High Uptake and Selectivity for CO2 due to Multiple CO2‐Philic Sites

The reaction of N‐rich pyrazinyl triazolyl carboxyl ligand 3‐(4‐carboxylbenzene)‐5‐(2‐pyrazinyl)‐1H‐1,2,4‐triazole (H₂cbptz) with MnCl₂ afforded 3D cationic metal–organic framework (MOF) [Mn₂(Hcbptz)₂(Cl)(H₂O)]Cl ? DMF ? 0.5 CH₃CN ( 1 ), which has an unusual (3,4)‐connected 3,4T1 topology and 1D channels composed of cavities. MOF 1 has a very polar framework that contains exposed metal sites, uncoordinated N atoms, narrow channels, and Cl^? basic sites, which lead to not only high CO₂ uptake, but also remarkably selective adsorption of CO₂ over N₂ and CH₄ at 298–333 K. The multiple CO₂‐philic sites were identified by grand canonical Monte Carlo simulations. Moreover, 1 shows excellent stability in natural air environment. These advantages make 1 a very promising candidate in post‐combustion CO₂ capture, natural‐gas upgrading, and landfill gas‐purification processes.     

Assembly of Three 2D Metal‐Organic Frameworks (MOFs) Derived from Flexible Ligands, 1,4‐bis(3‐pyridyl)‐2,3‐diaza‐1,3‐butadiene (3‐bpd) and/or 1,2‐bis(4‐pyridyl)ethane (dpe)

Three coordination polymers, {[Cd(3‐bpd)₂(NCS)₂]×C₂H₅OH}_n ( 1 ), {[Cd(3‐bpd)(dpe)(NO₃)₂]×(3‐bpd)}₂ ( 2 ), {[Cd(dpe)₂(NCS)₂]×3‐bpd×2H₂O}_n ( 3 ) (3‐bpd = 1,4‐bis(3‐pyridyl)‐2,3‐diaza‐1,3‐butadiene; dpe = 1,2‐bis(4‐pyridyl)ethane), were prepared and structurally characterized by a single‐crystal X‐ray diffraction method. In compound 1 , each Cd(II) ion is six‐coordinate bonded to six nitrogen atoms from four 3‐bpd and two NCS^? ligands. The 3‐bpd acts as a bridging ligand connecting the Cd(II) ion to generate a 2D layered metal‐organic framework (MOF) by using a rhomboidal‐grid as the basic building units with the 4⁴ topology. In compound 2 , the Cd(II) ion is also six‐coordinate bonded to four nitrogen atoms of two 3‐bpd, two dpe and two oxygen atoms of two NO₃^? ligands. The 3‐bpd and dpe ligands both adopt bis‐monodentate coordination mode connecting the Cd(II) ions to generate a 2D layered MOF by using a rectangle‐grid as the basic building units with the 4⁴ topology. In compound 3 , two crystallographically independent Cd(II) ions are both coordinated by four nitrogen atoms of dpe ligands in the basal plane and two nitrogen atom of NCS^? in the axial sites. The dpe acts as a bridging ligand to connect the Cd(II) ions forming a 2D interpenetrating MOFs by using a square‐grid as the basic unit with the 4⁴ topology. All of their 2D layered MOFs in compounds 1 ‐ 3 are then arranged in a parallel non‐interpenetrating ABAB—packing manner in 1 and 2 , and mutually interpenetrating manner in 3 , respectively, to extend their 3D supramolecular architectures with their 1D pores intercalated with solvent (ethanol in 1 or H₂O in 3 ) or free 3‐bpd molecules in 2 and 3 , respectively. The photoluminescence measurements of 1 ‐ 3 reveal that the emission is tentatively assigned to originate from π‐π* transition for 1 and 2 and probably due to ligand‐center luminescence for compounds 3 , respectively.     

Selective Sensing of Fe3+ and Al3+ Ions and Detection of 2,4,6‐Trinitrophenol by a Water‐Stable Terbium‐Based Metal–Organic Framework

A water‐stable luminescent terbium‐based metal–organic framework (MOF), {[Tb(L₁)_1.5(H₂O)] ? 3 H₂O}_n (Tb‐MOF), with rod‐shaped secondary building units (SBUs) and honeycomb‐type tubular channels has been synthesized and structurally characterized by single‐crystal X‐ray diffraction. The high green emission intensity and the microporous nature of the Tb‐MOF indicate that it can potentially be used as a luminescent sensor. In this work, we show that Tb‐MOF can selectively sense Fe³⁺ and Al³⁺ ions from mixed metal ions in water through different detection mechanisms. In addition, it also exhibits high sensitivity for 2,4,6‐trinitrophenol (TNP) in the presence of other nitro aromatic compounds in aqueous solution by luminescence quenching experiments.     

Multiscale Computational Study on the Adsorption and Separation of CO2/CH4 and CO2/H2 on Li+‐Doped Mixed‐Ligand Metal–Organic Framework Zn2(NDC)2(diPyNI)

The quantum mechanics (QM) method and grand canonical Monte Carlo (GCMC) simulations are used to study the effect of lithium cation doping on the adsorption and separation of CO₂, CH₄, and H₂ on a twofold interwoven metal–organic framework (MOF), Zn₂(NDC)₂(diPyNI) (NDC=2,6‐naphthalenedicarboxylate; diPyNI=N,N′‐di‐(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide). Second‐order Moller–Plesset (MP2) calculations on the (Li⁺–diPyNI) cluster model show that the energetically most favorable lithium binding site is above the pyridine ring side at a distance of 1.817 Å from the oxygen atom. The results reveal that the adsorption capacity of Zn₂(NDC)₂(diPyNI) for carbon dioxide is higher than those of hydrogen and methane at room temperature. Furthermore, GCMC simulations on the structures obtained from QM calculations predict that the Li⁺‐doped MOF has higher adsorption capacities than the nondoped MOF, especially at low pressures. In addition, the probability density distribution plots reveal that CO₂, CH₄, and H₂ molecules accumulate close to the Li cation site. The selectivity results indicate that CO₂/H₂ selectivity values in Zn₂(NDC)₂(diPyNI) are higher than those of CO₂/CH₄. The selectivity of CO₂ over CH₄ on Li⁺‐doped Zn₂(NDC)₂(diPyNI) is improved relative to the nondoped MOF.