Three-dimensional Open-framework Structure Research Articles

Solvent-free synthesis of new metal phosphites with double-layered, pillared-layered, and framework structures

Three new metal phosphites, formulated as (H3O)2·Mn2(HPO3)3 (1), Co(bpy) (H2O) (HPO3) (2), and H2tmpda·Zn3(HPO3)4 (3), have been synthesized under solvent-free conditions, where bpy = 4,4′-bipyridine, and tmpda = N,N,N′,N′-tetramethyl-1,3-propanediamine. Compound 1 has a double-layered structure with a thickness of 5.68 Å. Compound 2 has an inorganic-organic hybrid framework with cobalt phosphite layers pillared by bpy ligands. Compound 3 has a three-dimensional open-framework structure containing 8-ring channels. The temperature dependence of the magnetic susceptibility of compounds 1 and 2 were also investigated.

From an Open Framework to a Layered and a Hexagonal Tungsten Oxide Structure: Controlled Transformation Reactions of an Extended Solid-State Material, Cs3Ga7(SeO3)12 to Ga(OH)(SeO3) and KGa3(SeO4)2(OH)6

A highly symmetric open-framework gallium selenite, Cs3Ga7(SeO3)12, containing cubic superlattices has been synthesized by a standard solid-state reaction using Cs2CO3, Ga2O3, and SeO2 as reagents. Cs3Ga7(SeO3)12 exhibits a three-dimensional open-framework structure consisting of GaO4 tetrahedra, GaO6 octahedra, and SeO3 polyhedra. Step-by-step reactions of the solid-state material in aqueous KNO3 solution at different temperatures produce Ga(OH)(SeO3) with a layered structure and KGa3(SeO4)2(OH)6 having a hexagonal tungsten oxide (HTO) topology. Novel HTO layers capped by Se(6+) cations in KGa3(SeO4)2(OH)6 led us to synthesize other alkali metal gallium selenates, NaGa3(SeO4)2(OH)6 and RbGa3(SeO4)2(OH)6, using hydrothermal reactions. Thermal analyses, infrared spectroscopy, elemental analyses, and dipole moment calculations for the reported materials are also presented.

A Flexible Hexacarboxylate-Samarium(III) Metal–Organic Framework: Synthesis, Structure and Spectroscopic Properties

A new flexible triazine-based polycarboxylate metal–organic framework, [Sm2(TTHA)(H2O)4]·9H2O (I) (TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetate), has been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis and FT-IR spectroscopy. Crystal data for I are monoclinic C2/c, a = 12.6974(13) A, b = 16.7309(12) A, c = 14.8076(15) A, β = 91.452(8)°, V = 3,144.7(5) A3. Each SmIII ion is 9-coordinate in a distorted tri-capped trigonal prismatic geometry; but, the principal inorganic building block is {Sm2O16}, which comprises two of these polyhedra that share an edge. The complex exhibits a three-dimensional open-framework structure of approximately 31 % void volume, which comprises two types of channels oriented in three directions; [0 0 1], [1 1 0] and [−1 1 0]. The network can be simplified into either the cooperite (pts) or anatase (ant) topologies depending on the choice of nodes. The UV–Vis spectra of the compound are dominated by the absorption of the TTHA ligand. Thermogravimetric analysis shows that the loss of channel and coordinated water upon heating occurs in two distinct steps.

Cobalt phosphonates based on 4-(ethoxycarbonyl)naphthalen-1-yl)phosphonic acid

The first examples of metal phosphonates based on 4-(ethoxycarbonyl)naphthanen-1-yl)phosphonic acid (4-cnppH2) are reported, namely, Co(4-cnpp) (1), Co2(4-cnpp)2(dptz) (2) and Co2(4-cnpp)2(4,4'-bpy)(H2O) (3) (dptz = 3,6-di(pyridin-3-yl)-1,2,4,5-tetrazine, 4,4'-bpy = 4,4'-bipyridine). The cobalt atoms are four-coordinated with distorted tetrahedral geometries in both 1 and 2, while five-coordinated with a distorted trigonal bipyramidal environment in compound 3. Compound 1 shows a layer structure in which the inorganic layers made up of edge-sharing {CoNO3} dimers and {PO3C} linkages are separated by the organic groups of the 4-cnpp(2-) ligands. Compound 2 displays a different type of layer structure, where the ladder-like chains composed of corner-sharing {CoNO3} and {PO3C} tetrahedra are connected by dptz ligands with the organic groups of the 4-cnpp(2-) ligands pendent on the two sides of the layer. In 3, similar ladder-like chains of corner-sharing {CoNO4} and {PO3C} are also found except that the cobalt atoms within the chain are further bridged by a coordinated water molecule. The chains are cross-linked by 4,4'-bpy, leading to a three-dimensional open-framework structure. Magnetic studies reveal that dominant antiferromagnetic interactions are mediated between the Co(II) ions in all three cases.

Synthesis, crystal structures and properties of lanthanide-organic frameworks based benzene carboxylates with two/three-dimensional structure

A series of lanthanide coordination polymers, {[Dy3(1,3-BDC)4(NO3)(phen)3]·2H2O}n (1), {[Dy2(1,3-BDC)3(H2O)2]·H2O}n (2), {[Ln4(1,3-BDC)6(DMF)(H2O)4]·DMF·2H2O}n (Ln=Tb (3), Ho (4), Er (5), 1,3-H2BDC=1,3-benzenedicarboxylate, phen=1,10-phenanthroline, DMF=N,N-dimethylformamide), have been synthesized and characterized. In coordination polymer 1, each Dy3+ ion is connected to its neighboring Dy3+ ion through bridging carboxyl oxygen atoms of the 1,3-BDC2− ligands to form a new three-dimensional open-framework structure which the Schläfli symbol of {64·82}2{66}. In coordination polymer 2, center metal dysprosium ions are interlaced and connected through bridging carboxyl oxygen atoms to form an infinite helix chain. Two helix chains are linked through the 1,3-BDC2− ligand to give rise to the two-dimensional layered structure. Coordination polymers 3–5 are isomorphous, which displays a (3,4)-connected net with the point symbol of {42·63·8}{42·6}. The solid-state photoluminescence properties and lifetimes of the Dy (1 and 2) and Tb (3) coordination polymers have been measured at room temperature.

Role of boron-containing ionic liquid in the synthesis of manganese borophosphate with extra-large 16-ring pore openings

An open-framework manganese borophosphate (NH 4) 7Mn 4(H 2O)[B 2P 4O 15(OH) 2] 2[H 2PO 4][HPO 4] ( 1) has been synthesized by using 1-butyl-3-methyl-imidazolium bis(oxalato)borate ([C 4mim][BOB]) ionic liquid as a boron source, and characterized by X-ray powder diffraction (XRD), inductively coupled plasma (ICP), element analysis, thermogravimetric analysis and differential scanning calorimetry (TG–DSC). Single-crystal X-ray diffraction analysis shows that compound 1 crystallizes in orthorhombic space group Pnma (No. 62), a = 17.102(2) Å, b = 10.7195(15) Å, c = 22.283(3) Å, V = 4085.0(10) Å 3 and Z = 4. Its structure features an interrupted three-dimensional (3D) open-framework structure built up from [B 2P 4O 15(OH) 2] 6− borophosphate anions, Mn 2O 10 dimers and H x PO 4 3 - x ( x = 1, 2) groups, where peanut shaped extra-large 16-ring channels can be found extending along the [0 1 0] direction. Protonated NH 3 molecules locate in the void space to balance the negative charges of the inorganic framework. Magnetic measurements indicate that antiferromagnetic interactions exist between Mn 2+ ions with a negative Weiss constant of −18.2 K. The synthesis condition and various impact factors were studied carefully, which indicates that [BOB] anion of ionic liquid and acidity of the system are two important keys for the formation of the title compound.

Synthesis and crystal structure of a new MOF-type indium pyromellitate (MIL-117) with infinite chains of unusual cis connection of octahedra InO 4(OH) 2

A new MOF-type indium pyromellitate (MIL-117) was hydrothermally synthesized at 483 K for 24 h. The structure of MIL-117 with structural formula In 6(OH) 6(btec) 3(H 4btec)·8–14H 2O (btec = 1,2,4,5-benzenetetracarboxylate), orthorhombic ( Pnmm) symmetry and unit cell parameters a = 8.2390(8), b = 22.251(2), c = 37.791(4) Å, V = 6928.2(11) Å 3 was solved from single-crystal diffraction data. The three-dimensional open framework structure consists of infinite chains of unusual cis sharing In-centered octahedra linked to each other through the pyromellitate ligands. The three distinct In(III) cations are coordinated to four oxygen atoms from carboxyl groups and two μ 2-hydroxyl groups in cis positions. The MIL-117 network delimits one-dimensional channels of 7.7 × 8.0 Å running along the a axis, where occluded water molecules are located. Although water species can be easily removed from the pore, no significant N 2 or CO 2 sorption was observed.

Synthesis and crystal structure of a new open-framework iron phosphate (NH 4) 4Fe 3(OH) 2F 2[H 3(PO 4) 4]: Novel linear trimer of corner-sharing Fe(III) octahedra

A new iron phosphate (NH 4) 4Fe 3(OH) 2F 2[H 3(PO 4) 4] has been synthesized hydrothermally at HF concentrations from 0.5 to 1.2 mL. Single-crystal X-ray diffraction analysis reveals its three-dimensional open-framework structure (monoclinic, space group P2 1 /n (No. 14), a=6.2614(13) Å, b=9.844(2) Å, c=14.271(3) Å, β=92.11(1)°, V=879.0(3) Å 3). This structure is built from isolated linear trimers of corner-sharing Fe(III) octahedra, which are linked by (PO 4) groups to form ten-membered-ring channels along [1 0 0]. This isolated, linear trimer of corner-sharing Fe(III) octahedra, [(FeO 4) 3(OH) 2F 2], is new and adds to the diverse linkages of Fe polyhedra as secondary building units in iron phosphates. The trivalent iron at octahedral sites for the title compound has been confirmed by synchrotron Fe K-edge XANES spectra and magnetic measurements. Magnetic measurements also show that this compound exhibit a strong antiferromagnetic exchange below T N=17 K, consistent with superexchange interactions expected for the linear trimer of ferric octahedra with the Fe–F–Fe angle of 132.5°.

Metal diphosphonates with double-layer and pillared layered structures based on N-cyclohexylaminomethanediphosphonate

Based on N-cyclohexylaminomethanediphosphonic acid (cmdpH 4), four new metal diphosphonate compounds with formula M 3(cmdpH) 2(H 2O) 2 [ M=Zn( 1), Co( 2)] and M 2(cmdpH 2) 2(4,4′-bipy) 0.5(H 2O) [ M=Co( 3), Mn( 4)] have been obtained and structurally determined. Compounds 1 and 2 are isostructural. Within the structure, the M(2)O 6 octahedra are each corner-shared with four PO 3C tetrahedra to form a single layer containing 3- and 7-member rings. Neighboring single layers are pillared by M(1)O 4 tetrahedra, resulting in a novel double-layer structure. The organic moieties of cmdpH 3− are grafted on the two sides of the double layer. Compounds 3 and 4 are also isostructural, displaying a pillared layered structure. Within the inorganic layer, the M(1)O 5 tetragonal pyramids and M(2)NO 5 octahedra are each linked by PO 3C tetrahedra through corner-sharing, forming a layer in the ab plane which contains 3- and 10-member rings. These layers are pillared by 4,4′-bipyridine via coordination with the M(2) atoms from the adjacent layers, leading to a three-dimensional open framework structure with channels generated along the a-axis. The organic groups of cmdpH 2 2− locate within the channels. Magnetic studies show that antiferromagnetic interactions are dominant in compounds 2–4. Field dependent magnetization reveals a spin flop behavior for 2.

Two organic–inorganic hybrid frameworks with helical structures and large cavities constructed from poly(oxomolybdophosphates)

Two novel poly(oxomolybdophosphates) have been synthesized hydrothermally and characterized by single-crystal X-ray diffraction, IR spectroscopy, TG analysis, cyclic voltammetry, and magnetic susceptibility. In compound 1, the bbi ligands form a series of unusual one-dimensional pores with large apertures through the π⋯π stacking and hydrogen bonding interactions, meanwhile, the right- and left-hand helical chains are constructed from the Mn[P4Mo6]2-type secondary building units that are interspersed in the one-dimensional pore. Compound 2 exhibits a three-dimensional open-framework structure with large cavities where the protonated molecules of ethylenediamine and dissociative water molecules are located.

Lanthanide Carboxyphosphonates Ln(O3PCH2−NC5H9−COO)(H2O)2·xH2O with Open Framework Structures Containing Parallelogram-like Channels

On the basis of (4-carboxypiperidyl)-N-methylenephosphonic acid (4-cpmpH3), four isostructural lanthanide phosphonates Ln(O3PCH2−NC5H9−COO)(H2O)2·xH2O [Ln = Eu(1), Gd(2), Tb(3), Dy(4)] have been synthesized. All exhibit three-dimensional open framework structures, in which inorganic double chains made up of {Ln2O14} dimers and {PO3C} linkages are connected through organic moieties of 4-cpmp3−. Uniform parallelogram-like channels are observed in the [100] direction. Luminescent properties of 1 and 3, and the magnetic properties of 2 are investigated.

Transformation of a Layered Zinc Phosphite to a Three-Dimensional Open-Framework Structure with Intersecting 16- and 12-Ring Channels

A new layered zinc phosphite, H(2)tmdp x Zn(3)(HPO(3))(4) (tmdp = 4,4'-trimethylenedipiperidine), was prepared in a flux of phosphorous acid without the addition of water as a solvent. The compound could be transformed into a new three-dimensional open-framework zinc phosphite, Zn(2)(H(2)O)(4)(HPO(3))(2) x H(2)O, with intersecting 16- and 12-ring channels at room temperature.

Poly[hemi(ethylenediammonium) [di-μ-oxalato-indium(III)] dihydrate

In title compound, {(C2H10N2)0.5[In(C2O4)2]·2H2O}n, the unique InIII ion is coordinated by eight O atoms from four oxalate ligands in a distorted square-anti­prismatic environment. The doubly bis-chelating oxalate ligands act as bridging ligands connecting symmetry-related InIII ions and forming a three-dimensional open framework structure. Ethyl­enediammonium cations and water mol­ecules occupy the voids within the structure. The unique ethyl­enediammonium cation and one water mol­ecule both lie on a twofold rotation axis. One of the other two water mol­ecules residing on general crystallographic sites was refined as disordered with half occupancy. In the crystal structure, cations and water mol­ecules are linked to the anionic framework via inter­molecular O—H⋯O and N—H⋯O hydrogen bonds.

Synthesis, crystal structures and luminescence properties of lanthanide oxalatophosphonates with a three-dimensional framework structure

Six new three-dimensional (3D) lanthanide oxalatophosphonates, [Ln(HL)(C2O4)0.5(H2O)2]·H2O (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6); H3L = H2O3PCH(OH)CO2H), have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction as well as by infrared spectroscopy, elemental analysis and thermogravimetric analysis. Compounds 1–6 are isomorphous and they exhibit a complex three-dimensional (3D) open-framework structure with a one-dimensional channel system along the c-axis. The interconnection of the lanthanide(III) ions by phosphonate ligands results in a lanthanide phosphonate layer, and these layers are further bridged by oxalate anions to form a 3D open-framework. Compound 6 shows strong red luminescence in the solid state at room temperature.

Na5(NH4)Mn3[B9P6O33(OH)3]·1.5H2O

The overall hexa­gonal framework of the title compound, penta­sodium ammonium trimanganese(II) borophosphate sesquihydrate, consists of tube-like borophosphate anions, ∞ 1{[B3P2O11(OH)]4−}, made up of corner-sharing PO4 and BO4 tetra­hedra and BO2(OH) triangles, forming ten-membered ring windows. The tubes are inter­connected via distorted MnO6 octa­hedra, establishing a three-dimensional open-framework structure with two different types of ring-channels (12- and six-membered) that run along [001]. The 12-membered ring channels are occupied by NH4 + ions and water mol­ecules. The ten-membered ring windows in the walls of the tubes are occupied by Na+ ions. The remaining Na+ ions and the water mol­ecules, one of which is half-occupied, reside within the six-membered ring channels. The structural setup is consolidated by an O—H⋯O hydrogen bond between the OH group and an opposite O atom of the framework. Donor–acceptor distances ranging from 2.80 to 3.35 Å between the ammonium N atom, water O atoms and framework O atoms indicate further hydrogen-bonding inter­actions.

Synthesis, structures and photoluminescence of two Er(III) coordination polymers

Two new erbium compounds, [Er2(BDC)3(DMF)2] (1) and [Er2(CQC)3(DMF)3(H2O)] · DMF · H2O (2), where BDC stands for 1,4-benzenedicarboxylate, CQC for 2-(4-carboxyquinolin-2-yl)quinoline-4-carboxylate, and DMF for N,N-dimethylformamide, have been synthesized through pre-heating and cooling-down crystallization. In 1 the Er(III) is seven-coordinate with oxygen atoms from six BDC and one DMF, forming a three-dimensional open-framework structure. Compound 2 possesses a 2D structure based on dinuclear Er(III) building units. The photoluminescence of 1 has also been investigated.

Synthesis and Characterization of Four Metal−Organophosphonates with One-, Two-, and Three-Dimensional Structures

A series of metal-organic hybrid compounds were synthesized using two new phosphonic acids, pyridyl-4-phosphonic acid and p-xylylenediphosphonic acid (H(2)O(3)PCH(2)C(6)H(4)CH(2)PO(3)H(2)). The phosphonic acid ligands have been synthesized from their corresponding bromides following two different types of reactions. The reaction of pyridyl-4-phosphonic acid with three different divalent metal salts results in the formation of molecular structures of different dimensionality. The reaction of Cu(II) with the phosphonic acid under hydrothermal conditions yields a three-dimensional (3D) open framework structure having the molecular formula [Cu(4)(NC(5)H(4)-PO(3))(4)(H(2)O)(10)] (1). The reactions with Mn(II) and Zn(II) salts with the same phosphonic acid resulted in a two-dimensional layered and a dinuclear compound with molecular formulas [Mn(3)(NC(5)H(4)-PO(3))(4)(H(2)O)(6)(ClO(4))(2)] (2) and [Zn(2)(NHC(5)H(4)-PO(3)H)(2)Cl(4)] (3), respectively. Compound 1 crystallizes in the triclinic crystal system having space group P with structural parameters a = 7.4564(15) Angstrom, b = 9.1845(19) Angstrom, c = 11.582(2) Angstrom, alpha = 100.842(3) degrees, beta = 104.303(3) degrees, gamma = 94.774(3) degrees, and Z = 1. Compound 2 crystallizes in the triclinic crystal system, space group P, with structural parameters a = 7.6871(14) Angstrom, b = 10.576(2) Angstrom, c = 14.470(3)Angstrom, alpha = 81.340(3) degrees, beta = 81.561(3) degrees, gamma = 68.757(3) degrees, and Z = 2, whereas compound 3 crystallizes in a monoclinic crystal system with space group P2(1)/n. The structural parameters are as follows: a = 8.4969 (5) Angstrom, b = 9.3911 (5) Angstrom, c = 12.3779 (6) Angstrom, beta = 90.860(17) degrees, and Z = 4. The pyridylphosphonate ligand shows different ligation behavior toward the three divalent metal ions. On the other hand, p-xylylenediphosphonic acid on reaction with Co(II) formed a 3D compound [Co(2)(O(3)PCH(2)C(6)H(4)CH(2)PO(3))(2)(H(2)O)(2)] (4) with a layered and pillared structure. Compound 4 crystallizes in an orthorhombic crystal system with space group Pnma. The structural parameters are a = 21.744(4) Angstrom, b = 5.6744(10) Angstrom, c = 4.7927(9) Angstrom, and Z = 4.

(C5H14N2) [Zn3(HPO4)4], a New 3D Open‐Framework Zincophosphate Synthesized by Hydrothermal Reversible Transformation of (C5H14N2) [Zn2(HPO4)3]×H2O.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Heavy‐Metal‐Ion Capture, Ion‐Exchange, and Exceptional Acid Stability of the Open‐Framework Chalcogenide (NH4)4In12Se20

The hydrothermal synthesis of the purely inorganic open-framework indium selenide (NH(4))(4)In(12)Se(20) (1) is reported. Compound 1 exhibits a unique three-dimensional open-framework structure. The framework of 1 shows an unusual, for a chalcogenide compound, rigidity arising from the unprecedented connection mode of its building blocks. Compound 1 possesses ion exchange capacity for Cs(+), Rb(+), NH(4) (+), but it has selectivity against Na(+) and Li(+). It also showed exceptional stability in relatively concentrated hydrochloric acid. Ion exchange of 1 with hydrochloric water solutions can produce its solid acid analogue H(2)(NH(4))(2)In(12)Se(20). The maximum cation-exchange capacity of 1 was found equal to two equivalents per mol, which is consistent with an exchange mechanism taking place in the 1D-channels formed by the largest cavities. In addition, 1 can do ion-exchange with heavy-metal ions like Hg(2+), Pb(2+), and Ag(+). The capacity of 1 to clean water solutions from heavy-metal ions was preliminarily investigated and found very high. Specifically, 1 can remove 99.9 % of Hg(2+), 99.8 % of Ag(+), and 94.9 % of Pb(2+) from aqueous solutions of each of these ions. Using different synthetic conditions, we isolated compound (NH(4))(2)In(12)Se(19) (2), which also has as good an acid stability as 1, but no ion-exchange properties. Overall, this work provides new hydrothermal synthetic approaches for isolation of all-inorganic open-framework chalcogenides.

Synthesis, Structure and Luminescence Property of Two Lanthanum Phosphite Hydrates: La2(H2O)x(HPO3)3 (x = 1, 2).

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.