3D Open-framework Structure Research Articles

Cu12-cluster-based metal-organic framework as a metastable intermediate in the formation of a layered copper phosphonate.

The solvothermal reaction of CuSO4·5H2O and a chiral R-pempH2 ligand (molar ratio 6 : 1) first forms the metastable intermediate [Cu24(OH)20(R-pempH)8(SO4)10(H2O)10.5]·35H2O (1), followed by the formation of the stable phase [Cu2(OH)(R-pempH)(SO4)(H2O)]·H2O (2). Compound 1 displays a novel 3D open-framework structure containing Cu12 cluster nodes and sulfate links, which can be converted to the layered compound 2. We also investigated the photothermal effects of both compounds.

Influence of separator and bimetallic doping on Zn2+ ion storage properties of Prussian blue analogues for aqueous zinc-ion batteries

Prussian blue analogues (PBA) have been gaining attention as cathode materials for Aqueous zinc-ion batteries (AZIBs) owing to their 3D open framework structure; however, they suffer from low specific capacity, fast degradation, and poor cycling stability. In this study, we report Co–Ni co-doped PBA, with different Co and Ni ratios with high purity and crystallinity as cathode materials for AZIBs. Moreover, different low-cost porous water-based separators are proposed in conjunction with Co–Ni co-doped PBA cathodes. The studies on Zn||Zn symmetric cell show that nitrocellulose membrane (NC) separator can operate over 2000 h with lower hysteresis voltage of 90 mV and considerably decreases the dendrite grown on the Zn-metal surface due to the uniform pore size distribution. Benefiting from the synergetic effect of bimetallic doping and Zn dendrite inhibition ability from NC separator, the aqueous K1.9Co0.67Ni0.33[Fe(CN)6].1.7H2O||Zn cell is able to display excellent cycling performance of 5000 cycles at 1 A g−1 with a maximum capacity retention of 84 %. This research not only demonstrates the considerable effect of bimetallic doping on the Zn storage performance of PBA cathodes, but it also discloses the influence of separator on the zinc striping/plating process, which will provide insights into the development of high-performance AZIBs.

Boosting the proton conduction in a magnetic dysprosium-organic framework by introducing conjugate NH4+-NH3 pairs

Metal-organic frameworks (MOFs) with inherent porosity and suspended acidic groups are promising proton conducting materials in water or aqua-ammonia media. Herein we report a new lanthanide phosphonate, namely, Dy2(amp2H2)2(mal)(H2O)2·5H2O (MDAF-6). It possesses a 3D open-framework structure, and shows a high NH3 adsorption capacity of 142.4 cm3/g at P/P0 = 0.98 at 298 K due to acid-base interaction. Interestingly, the proton conductivity of MDAF-6-NH3 is enhanced by five orders of magnitude compared to MDAF-6 after 8.5 h exposure in saturated NH3-H2O vapor, indicating the importance of coexistent conjugate acid-base pairs of H3O+-H2O and NH4+-NH3 in promoting proton conduction. Magnetic studies of MDAF-6 revealed slow magnetization relaxation under zero dc field, characteristic of single-molecule magnet behavior. This work provides not only a new multifunctional MOF material, but also a new strategy to improve proton conduction in aqua-ammonia medium.

A Seamless Metal-Organic Framework Interphase with Boosted Zn2+ Flux and Deposition Kinetics for Long-Living Rechargeable Zn Batteries.

Zn metal has received immense interest as a promising anode of rechargeable aqueous batteries for grid-scale energy storage. Nevertheless, the uncontrollable dendrite growth and surface parasitic reactions greatly retard its practical implementation. Herein, we demonstrate a seamless and multifunctional metal-organic framework (MOF) interphase for building corrosion-free and dendrite-free Zn anodes. The on-site coordinated MOF interphase with 3D open framework structure could function as a highly zincophilic mediator and ion sifter that synergistically induces fast and uniform Zn nucleation/deposition. In addition, the surface corrosion and hydrogen evolution are significantly suppressed by the interface shielding of the seamless interphase. An ultrastable Zn plating/stripping is achieved with elevated Coulombic efficiency of 99.2% over 1000 cycles and prolonged lifetime of 1100 h at 10 mA cm-2 with a high cumulative plated capacity of 5.5 Ah cm-2. Moreover, the modified Zn anode assures the MnO2-based full cells with superior rate and cycling performance.

Unlocking fast and highly reversible sodium storage in Fe-based mixed polyanion cathodes for low-cost and high-performance sodium-ion batteries

The iron-based polyanionic material Na3Fe2(PO4)P2O7is regarded as an excellent cathode due to its outstanding thermal stability and the three-dimensional (3D) open framework structure with facile sodium-ion transport.

Mixed-ligated cobalt phosphonates showing slow magnetic relaxation and spin-flop behavior

Metal-organic frameworks or coordination polymers showing interesting magnetic properties have attracted much attention. By using 4,4′-bipyridine (4,4′-bpy) as auxiliary ligand, three new cobalt phosphonates based on 1-naphthalene phosphonic acid (1-napH2) were assembled under hydrothermal conditions at different pH, namely, Co(1-napH)2(4,4′-bpy)2(H2O)2 (1), Co2(1-nap)2(4,4′-bpy) (2), and Co2(1-nap)2(4,4′-bpy)(H2O)·2H2O (3). Compound 1 has a 0D mononuclear structure, where the Co(II) ion has a distorted octahedral geometry and 4,4′-bpy serves as an unusual terminal ligand. A 2D layer structure is found in compound 2, where the ladder-like chains made up of corner-sharing CoO3N and PO3C tetrahedra are connected by 4,4′-bpy. Interestingly, compound 3 with similar chemical composition to 2 except additional water molecules shows a 3D open-framework structure, where undulating chains of corner-sharing CoO4N trigonal bipyramids and PO3C tetrahedra are cross-linked by 4,4′-bpy. Magnetic studies reveal that compound 1 exhibits field-induced slow magnetization relaxation, whereas compounds 2 and 3 show field-induced spin-flop behavior and paramagnetism, respectively.

Genuine Pores in a Stable Zinc Phosphite for High H2 Adsorption and CO2 Capture.

An uncommon example of stable mixed-ligand zinc phosphite with genuine pores has been synthesized by using zinc metal, inorganic phosphite acid, thio-functionalized O-donor (2,5-thiophenedicarboxylate, TPDC), and tetradentate N-donor [1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene, TIMB] units assembled into one crystalline structure according to a hydro(solvo)thermal method. This is a very rare case of a metal phosphite incorporating both N- and O-donor ligands. The tetradentate TIMB linker bound to zinc atoms of the isolated zincophosphite hexamers to form a 3D open-framework structure by crosslinking structural components of 1D chains and 2D layers. Here, the TPDC ligand acts as a monodentate binding model to functionalize its porous structure with the uncoordinated S atom and COO- group. Interestingly, this compound demonstrates the highest H2 storage capacity among organic-inorganic hybrid metal phosphates (and phosphites), and a good CO2 capture at 298 K compared with the majority of crystalline materials. The possible adsorption sites and selectivity for CO2 over H2 , N2 , and CO at 298 K were calculated by using density functional theory (DFT), the ideal adsorption solution theory (IAST), and fitting experimental pure-component adsorption data.

Heterometallic uranyl-organic frameworks incorporating manganese and copper: Structures, ammonia sorption and magnetic properties

Incorporating transition metal ions into uranyl phosphonate frameworks can bring not only new structure types but also interesting physical or chemical properties. Herein we report two heterometallic uranyl carboxyphenylphosphonates, namely, [Cu2(UO2)3(2-pmbH)2(2-pmb)2(H2O)4]·2H2O (1) and [Mn3(UO2)6(2-pmb)6(H2O)8]·10H2O (2) [2-pmbH3 = 2-(phosphonomethyl)benzoic acid]. Compound 1 shows a two-dimensional layered structure in which uranyl-PO3 chains are linked by {Cu2O2} dimers. Within the uranyl-PO3 chain, {UO6} tetragonal bipyramids and edge-sharing dimers of {UO7} pentagonal bipyramids are connected by edge-sharing {PO3C} tetrahedra. Compound 2 possesses a unique 3D open framework structure, where the Mn-layers are pillared by uranyl-PO3 chains. The uranyl-PO3 chain in 2 is very different from that in 1, which contains trimers of edge-sharing {UO7} and {UO8} polyhedra and {PO3C} linkages. While the Mn-layer consists of chains of {MnO6} octahedra bridged alternatively by carboxylate and phosphonate groups, which are inter-connected by organic moieties of 2-pmb3-. The thermally activated sample of 2 displays strong adsorption capability toward NH3. Magnetic studies revealed dominant antiferromagnetic interactions between the metal centers in both compounds.

(Invited) Research Development on K-Ion Batteries

In recent years, K-ion batteries (KIBs) have attracted significant attention as potential alternatives to Li-ion batteries (LIBs). Previous studies have developed positive and negative electrode materials for KIBs and demonstrated several unique advantages of KIBs over LIBs and Na-ion batteries (NIBs). Besides being free from any scarce/toxic elements, the low standard electrode potentials of K/K+ electrodes lead to high operation voltages competitive to those observed in LIBs. Moreover, K+ ions exhibit faster ionic diffusion in electrolytes due to weaker interaction with solvents and anions than with Li+ ions; this is essential to realize high-power KIBs. Over the past few years, many potassium insertion materials have been evaluated in K cells. Figure 1 summarizes the yearly number of scientific papers on K batteries. The number of papers on K systems drastically increased in recent years. Thus, we have recently published a comprehensive review to provide a guideline for research on KIBs (1). This talk presents an overview of our recent development on electrode and electrolyte materials.Previous studies on positive electrode materials for KIBs have shed light on the importance of the crystal structures, redox center, and anions in the framework. Although transition metal layered oxides are the most promising positive electrode materials for LIBs and NIBs, we found that typical transition metal layered oxide materials like P2-K x CoO2 exhibit small capacities, low operating potentials, and multiple phase transitions due to K+/vacancy ordering (2). PBAs are one of a promising group of positive electrode materials in terms of energy density, cycle performance, and rate performance (3, 4). Their 3D open framework structure provides suitable channels and interstitial sites for large K+ ion diffusion and insertion. Interestingly, unlike layered transition metal oxides, PBAs tend to exhibit higher K+ ion insertion potentials than those of Li+ and Na+ ions (5). Similar to PBAs, polyanionic compounds with 3D open framework structures are other possible positive electrode material candidates, owing to their high ionic conductivities and high operation potentials. Previous studies have revealed suitable crystal structures, including the KTiOPO4-type structure for K+ ion diffusion (6). Moreover, an inorganic-organic hybrid material called metal organic phosphates open framework (MOPOF) has been demonstrated as a 4 V-class positive electrode for KIBs with high rate capability (7).For negative electrodes, graphite is a promising candidate for KIBs (8). Our current studies are confirming that the physical properties of graphite, such as the d002 and Lc values, affect the electrochemical performance and that the optimum properties should be different from those of the Li system. Therefore, the development of graphite material suitable for K+ insertion is also an interesting and practically important topic. Furthermore, many studies of negative electrode materials have highlighted the properties of SEI, which depend on the electrolyte composition; this is important to demonstrate satisfactory cycles and rate capabilities (1). Therefore, recent studies have been focusing on the development of suitable electrolytes. The use of proper electrolytes, such as superconcentrated KFSA electrolytes (9), dramatically improved the electrochemical performance of the positive and negative electrodes. Thus, we believe that the development of a suitable electrolyte for KIBs will achieve a breakthrough in the research field of KIBs. Based on these results, we will provide insights into electrode reactions and solid ionics and nonaqueous solution chemistry as well as perspectives on the research-based development of KIBs, compared to those of LIBs and NIBs.

Potassium cobalt hexacyanoferrate nanocubic assemblies for high-performance aqueous aluminum ion batteries

Prussian blue analogues are considered as a class of extremely promising electrode materials for various energy storage devices. Here, the potassium cobalt hexacyanoferrate (K2CoFe(CN)6) with a nanocubic assembled structure was successfully synthesized via a one-step hydrothermal method and low-temperature calcination operation; this material is employed as the working electrode for aqueous aluminum ion batteries (AIBs). To some extent, such a 3D open-framework structure accelerated the electronic and ionic transmission and optimized the electrochemical properties. The as-prepared K2CoFe(CN)6 demonstrated a reversible discharge capacity of 50 mA h g−1 at a of 0.1 A/g and showed a desirable cycling stability, which makes it a feasible electrode material for aqueous AIBs.

Conductometric acetone vapor sensor based on the use of gold-doped three-dimensional hierarchical porous zinc oxide microspheres.

A versatile nanoprobe for acetone vapor was designed and fabricated. It is based on the use of gold-doped three-dimensional (3D) hierarchical porous zinc oxide microspheres (Au/ZnO HPMSs). The nanoprobe was synthesized by annealing zinc hydroxide carbonate precursor (obtained by a hydrothermal method) doped with gold nanoparticles. The resulting products possess a 3D open framework structure built of 2D porous nanosheets with a nanoporous wormhole-like shape. The microspheres doped with 0.5mol% gold display a good selectivity towards acetone. The conductometric nanoprobe, typically operated at a voltage of 5V, can detect sub-ppm levels of acetone, and the detection limit is as low as 0.2ppm. The response (at a level of up to 100ppm of acetone at 325°C) was high (74 ± 1.9), and the response and recovery time are 6 and 3s, respectively. This superior performance is ascribed (a) to the hierarchical porous ZnO architecture that warrants a large surface area; and (b) to the presence of gold nanoparticles that facilitate the chemisorption and dissociation of gas molecules. Graphical abstract Gold-doped 3D hierarchical porous ZnO microspheres (Au/ZnO HPMSs) architectures assembled by interconnected 2D porous nanosheets structures. The resistive sensor using these Au/ZnO HPMSs demonstrates outstanding acetone vapor sensing behaviors and 0.2ppm detection limits.

Centrosymmetric (Hdima)2[Ge5B3O15(OH)] and Noncentrosymmetric Na4Ga3B4O12(OH): Solvothermal/Surfactant-Thermal Synthesis of Open-Framework Borogermanate and Galloborate.

Under solvothermal/surfactant-thermal conditions, two new open-framework borogermanate and galloborate, centrosymmetric (Hdima)2[Ge5B3O15(OH)] (1; dima = dimethylamine) and noncentrosymmetric Na4Ga3B4O12(OH) (2), were obtained and characterized. Compound 1 contains an unusual basket-shaped Ge5B3O18(OH) cluster and displays a 3D open-framework layered structure. Compound 2 shows an interrupted 3,4-connected network constructed by alternately linked BO3 units and Ga3+ ions and displays weak second-harmonic-generation response.

Structural Insights into Borates with an Anion-Templated Open-Framework Configuration: Asymmetric K2 BaB16 O26 versus Centrosymmetric K3 CsB20 O32 and Na2 M2 NB18 O30 (M=Rb, Cs; N=Ba, Pb).

Five new mixed-metal borate crystals, namely, K2 BaB16 O26 , K3 CsB20 O32 , Na2 Cs2 BaB18 O30 , Na2 Rb2 PbB18 O30 , and Na2 Cs2 PbB18 O30 , have been synthesized by the high-temperature solution method. These structures were characterized by single-crystal X-ray diffraction and their B-O configurations are shown to feature complicated three-dimensional (3D) open-framework structures incorporating different types of channels. For all five compounds, the frameworks can be reduced to four-connected (4-c) uninodal nets with sra-, dia- and nbo-type topologies by assigning the [B5 O10 ]5- and [B3 O7 ]5- clusters as basic nodes. First-principles calculations have shown that the multiple cations in mixed-metal borates influence the ground-state electronic structures and associated optical absorptions. In addition, the crystal structures, thermal stabilities, and IR spectra of the title compounds have also been performed.

Porous Uranyl Borophosphates with Unique Three-Dimensional Open-Framework Structures.

Two novel alkali-metal uranyl borophosphates have been prepared and characterized for the first time, namely, K5(UO2)2[B2P3O12(OH)]2(OH)(H2O)2 and K2(UO2)12[B(H2PO4)4](PO4)8(OH)(H2O)6 denoted as KUPB1 and KUPB2, respectively. KUPB1 was obtained hydrothermally at 220 °C and crystallizes in a monoclinic structure in the chiral space group P21. The unit cell parameters of KUPB1 are a = 6.7623(2) Å, b = 19.5584(7) Å, c = 11.0110(4) Å, α = γ = 90°, β = 95.579(3)°, and V = 1449.42(8) Å3. It features a unique three-dimensional (3D) open-framework structure, composed of two corner-sharing linked one-dimensional (1D) anionic borophosphates (BP), [B2P3O13]5-, along the a axis and uranyl phosphate (UP), [(UO2)(PO4)3]7-, chains along the c axis, further bridged by PO4 tetrahedra. Multi-intersectional channels can be observed within the structure, in which the largest 11-ring (11-R) tunnel size is ∼7.0 Å × 8.8 Å. Its simplified framework can be described as a new 4-nodal net topological type with a point symbol of {4.84.10}{42.6}2{43.62.83.102}{82.10}. By modification of the synthetic conditions of KUPB1 through an increase in the amount of H3BO3 as flux 4-fold and a reduction of water as the reaction medium, the novel compound KUPB2 is generated. The unit cell parameters of KUPB2 are a = b = 21.8747(3) Å, c = 7.0652(2) Å, α = β = γ = 90°, and V = 3380.72(12) Å3. KUPB2 crystallizes in a tetragonal structure in the polar space group I4̅2m, and its structure is based on a highly complex 3D framework, {(UO2)12[B(PO4)4](PO4)8}9-, in which 1D 8-R UP [(UO2)(PO4)]- tubes can be observed along the c axis. The [(UO2)(PO4)]- tubes consist of three uranyl chains along the c axis, which are linked alternately by [PO4]3- tetrahedra. Those isolated 1D [(UO2)(PO4)]- tubes are further bridged through [(UO2)4B(PO4)4]- clusters, forming an exceptional 3D open-framework structure. Its simplified cation network is a new 5-nodal net topological type such as {32.43.5.62.7.8}8{34.45.54.62}8{4.62.83}4{42.6}4{44.62}. Their facile hydrothermal synthetic routes, porous structure topology, thermal stability, and Raman spectroscopy properties are reported and discussed.

Syntheses, Crystal Structures, and Optical and Photocatalytic Properties of Four Small-Amine-Molecule-Directed M–Sn–Q (M = Zn, Ag; Q = S, Se) Compounds

By utilizing different small amine molecules as structure-affecting agents (SAAs) and charge-balancing agents (CBAs), four new M–Sn–Q (M = Zn, Ag; Q = S, Se) compounds with the anionic architectures ranging from a one-dimensional (1D) chain to a three-dimensional (3D) network have been solvothermally synthesized. Compound [(Me)2NH2]2ZnSn3Se8 (1) features an anionic (4,4) layer of [ZnSn3Se8]n2n– and represents a rare [ZnSn3Se10] T2 cluster-based two-dimensional Zn–Sn–Se compound directed by organic amine. Compound [NH4]3AgSn3Se8 (2) contains infinite linear anionic chains of [AgSn3Se8]n3n–. Compound [CH3NH3]2[H3O]Ag5Sn4Se12·C2H5OH (3) exhibits a 3D open-framework structure of [Ag5Sn4Se12]n3n– with intersecting 3D channels. Compound [CH3NH3]6Ag12Sn6S21 (4) features a 3D framework structure with 1D channels filled by [CH3NH3]+ cations. The most fascinating structural feature of compound 4 is that a complex 3D [Ag12S17]n22n– anionic network exists based on the combination of three types of basic building bloc...

Hydrothermal synthesis of two supramolecular inorganic–organic hybrid phosphomolybdates based on Ni(ii) and Co(ii) ions: structural diversity and heterogeneous catalytic activities

Two new compounds (NHEPH2)5[NiII(P4Mo6O31)2]·6H2O (1) and {(NHEPH2)2[CoII(H2O)6]}[P2Mo5O23]·2H2O (2) exhibited heterogeneous styrene oxidation by H2O2 under mild conditions.

Syntheses, crystal structures, and luminescent properties of three zinc carboxyphosphonates with 2D layered and 3D pillared-layer structures

Three zinc(II) carboxyphosphonates [Zn3(5-pmipe)2]·0.5H2O (1·0.5H2O), [Zn3(5-pmipm)2]·H2O (2·H2O), and [Zn3(5-pmipH)2(bpy)0.5]·6H2O (3·6H2O) (5-pmipH4=5-(phosphonomethyl)isophthalic acid, 5-pmipeH3=[C6H3(CO2H)(CO2Et)(CH2PO3H2)], 5-pmipmH3=[C6H3(CO2H)(CO2Me)(CH2PO3H2)], bpy=4,4′-bipyridine) were synthesized under hydrothermal conditions. Compounds 1 and 2 are isostructural. In compounds 1 and 2, the {ZnO4} and {CPO3} tetrahedra are interconnected into a zigzag infinite chain via corner-sharing. In addition, these chains are further linked by carboxyphosphonate ligands into a 2D layer. Interestingly, one carboxylate group experiences an in situ esterification reaction with ethanol and methanol, respectively. Compound 3 displays a 3D pillared-bilayer open framework structure. The {ZnO4}, {ZnO3N} and {CPO3} tetrahedra are interlinked through corner-sharing into one chain, which are joined together by 5-pmipH3− into a bilayer. The layers are pillared up by bpy into 3D network. The luminescent properties of compounds 1–3 were investigated in solid state at room temperature.

Observation of a Less Stable Conformer of N,N′‐Piperazine‐bis(methylenephosphonate) Ligand in a Six‐coordinated ­Samarium Phosphonate Framework

AbstractThe three‐dimensional (3D) samarium phosphonate framework [Sm2(H2L)3]n·5n(H2O) (1) [H4L = N,N′‐piperazine‐bis(methylenephosphonic acid)] was synthesized by hydrothermal reaction of Sm2O3 with N,N′‐piperazine‐bis(methylenephosphonic acid) hydrochloride in the presence of glutaric acid. Single‐crystal X‐ray diffraction analysis reveals that it has a 3D open framework structure with helical channels along the crystallographic c axis. The channels are filled up by discrete pentameric water clusters, which are hydrogen‐bonded to the host. Compound 1 displays two interesting structural features: (a) two of three H2L2– ligands adopt the less stable a,e‐cis conformation; (b) both of the SmIII ions exhibit rather unusual octahedral coordination arrangements. In addition, the photoluminescent property was investigated.

Synthesis, crystal structures, and luminescent properties of tin(II) and lead(II) carboxyphosphonates with 3D framework structures

Two new metal carboxyphosphonates with 3D framework structures, [Sn2(HL)·2H2O] (1) and [Pb2Cl(H2L)] (2) (H5L=4-HOOCC6H4CH2N(CH2PO3H2)2), have been synthesized under hydrothermal conditions. For compound 1, every two Sn(1)O3 and Sn(2)O3 polyhedra are linked by CPO3 tetrahedra to form a 2D inorganic layer via corner-sharing in the bc-plane. Then the adjacent layers are further assembled into a 3D supramolecular structure through π–π stacking interactions. Compound 2 features a 3D open-framework structure. The Pb(1)O5Cl, Pb(2)O5 polyhedra and CPO3 tetrahedra are interconnected into a 2D inorganic layer via corner-sharing in the ac-plane. Such layers are further connected through carboxyphosphonate ligands to form a 3D open-framework structure. The luminescent properties of compounds 1 and 2 have also been studied.

Polymorphic Ln(iii) and BPTC-based porous metal–organic frameworks with visible, NIR photoluminescent and magnetic properties

By reaction of 3,3′,5,5′-biphenyltetracarboxylic acid (H4BPTC) with various lanthanide ions, seven novel three dimensional (3D) lanthanide metal–organic frameworks (MOFs) have been prepared under solvothermal conditions, namely, [Ln3(BPTC)3(H2O)2]·3H3O·4H2O·3DMF (DMF = N,N-dimethylformamide, Ln = Eu (1), Tb (2), Sm (3) Dy (4)), [Nd(BPTC)(H2O)2]·H3O·DMF (5), [Er2(BPTC)(HCOO)3(H2O)2]·(CH3)2NH2 (6), and [Tm12(BPTC)8(HCOO)11(H2O)10]·10DMF·7(CH3)2NH2 (7). Combining different lanthanide ions and diversity of coordination modes of the H4BPTC ligand, the seven compounds display interesting structural characteristics. Of these, compounds 1–4 are isostructural and demonstrate a unique 3D coordination framework containing two types of 1D channel, that is built by the novel trinuclear [Ln3O22] SBUs. Compound 5 can be described as a new 3D open-framework structure with quadrilateral-shaped 1D channels based on [Nd2O16] SBUs. Compound 6 has a new 3D pillar network feature constructed by trapezoidal chains linked by bridging BPTC4− ligands, whilst compound 7 exhibits a 3D network with a number of rare oval-shaped channels along the [101] direction. The H4BPTC ligand exhibits five new coordination modes, which are firstly reported in M-BPTC frameworks. Compounds 1–7 all display their typical emission bands upon irradiation at the ligand band at room temperature. Compounds 1–4 present strong characteristic emissions in the visible region, of which compounds 1 and 2 show millisecond luminescence lifetimes. The NIR photoluminescent of lanthanide MOFs is less well observed, especially for the Tm(III) compounds. Owing to the good sensitization of the H4BPTC ligand, compounds 5–7 display near-infrared region (NIR) emission with microsecond luminescence lifetimes. In addition, compounds 2, 5, 6 and 7 exhibit global antiferromagnetic behaviors, of which compound 5 shows a weak ferromagnetic coupling at 235 K.