Zinc Phosphite Research Articles

A new hybrid zinc phosphite with a pillared layered structure: Synthesis and characterization of [C6N2O2H16][Zn(HPO3)

Abstract By using flexible 1,2-bis(2-aminoethoxy)ethane (BAEOE) as a pillaring ligand, a new inorganic–organic hybrid open-framework zinc phosphite, [C 6 N 2 O 2 H 16 ][Zn(HPO 3 )] 2 ( 1 ), has been hydrothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. The structure of 1 consists of neutral layers of zinc phosphite which are further pillared through linear BAEOE ligands, generating a 3D framework with unusual (3, 4)-connected dmc topology. The participation of left-handed and right-handed helical chains in the construction of puckered sheet structure with 4.8 2 -net is also noteworthy.

Synthesis and characterization of three-layered zinc phosphites containing tert-octylamine molecules with template and ligand roles

Three-layered zinc phosphites containing single monoamine molecules with different roles have been synthesized using hydro(solvo)thermal methods and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and infrared spectroscopy. Compound 1 , (C 8 H 17 NH 3 ) 4 Zn 3 (HPO 3 ) 5 ·3H 2 O, consists of 20-ring layer structures sandwiched by water molecules and protonated tert -octylamine molecules. The structure of Zn(C 8 H 17 NH 2 )(HPO 3 ) (compound 2 ) is composed of 4.8 2 network structures, wherein the tert -octylamines are coordinated to the Zn atom as pendant groups. Compound 3 , (C 8 H 17 NH 3 ) 2 Zn 4 (C 8 H 17 NH 2 )(HPO 3 ) 5 , was prepared in which the amine plays a dual role as both a ligand and a countercation. In addition, compound 1 is the first layered metal phosphite with large 20-ring windows. This group of substances represents the first example of the preparation of compounds in which the reactivity of incorporated single amine molecules is varied by adjusting the synthesis conditions. The first layered metal phosphite with large 20-ring windows, (C8H17NH3)4Zn3(HPO3)5·3H 2 O (1), sandwiched by water molecules and protonated tert -octylamine molecules. • The first example of zinc phosphites contains amine molecules with template and ligand roles. • The reactivity of single amine molecules is varied by adjusting the synthesis conditions. • Compound 1 contains the largest pore opening of 20-rings in known layered metal phosphites. • Compound 3 has dual roles of amine molecules in its structure.

An inorganic–organic hybrid zinc phosphite framework with unusual topology

Employing piperazine (= ppz) as a bridging ligand, a new three-dimensional (3D) inorganic–organic hybrid zinc phosphite framework [Zn 2 (HPO 3 ) 2 (ppz)] n ( 1 ) has been synthesized hydrothermally and structurally characterized by single crystal X-ray diffraction. The structure of 1 features a pillared-layer framework with unusual (3,4)-connected dmc topology. The results demonstrate that it is possible to add organic ligands into an open zinc phosphite framework for the construction of hybrid materials. Presented here is a new inorganic–organic hybrid zinc phosphite framework with unusual (3,4)-connected dmc topology. ► A new inorganic–organic hybrid zinc phosphite framework. ► A hybrid framework material with unusual (3,4)-connected dmc topology. ► Interesting pillared-layer structure assembled from inorganic layers and organic pillars.

In situ template generation via N-alkylation in the syntheses of open-framework zinc phosphites and phosphate

In methanol-aqueous solutions, three novel structure-directing agents (SDAs) were generated in situ and presented. These in situ reactions feature N-methylation transformations between CH3OH solvent and organic cyclic aliphatic and aromatic amines, i.e. 2-methylpiperazine, 1,4-diazabicyclo[2,2,2]octane (dabco) and 3-(aminomethyl)pyridine. Distinct from conventional Eschweiler-Clarke methylation containing excess formic acid and formaldehyde, such a direct methylation transformation from methanol molecules is unique. In the presence of new SDAs, three organically templated zinc phosphites/phosphates, [pmpip][Zn3(HPO3)4] I (pmpip = N,N,N',N'-tetramethyl-2-methylpiperazinium), [dmdabco][Zn3(HPO3)4] II (dmdabco = N,N'-dimethyl-1,4-diazabicyclo[2,2,2]octane) and [Hmampy][Zn2(HPO4)3] III (mampy = N-methyl-3-(aminomethyl)pyridine), have been prepared and structurally characterized by elemental analysis, IR, thermogravimetric analysis, powder and single-crystal X-ray diffraction. Compound I exhibits a 2D layer with eight-membered apertures, compounds II and III possess a 3D interrupted framework with intersecting 8-, 10- and 12-ring channels (for II), and 8-, 10-ring channels (for III), respectively.

ChemInform Abstract: Syntheses and Structures of Two Open‐Framework Zinc Phosphites with Extra‐Large 24‐Ring Channels.

AbstractThe new three‐dimensional open‐framework compounds (II) are solvothermally synthesized and characterized by single crystal XRD.

Controlled synthesis and mechanical properties of a highly flexible porous zinc phosphite

Controlled synthesis and mechanical properties of a highly flexible porous zinc phosphite

Syntheses and structures of two open-framework zinc phosphites with extra-large 24-ring channels

Two new three-dimensional open-framework zinc phosphites, [HCHA]2[Zn3(HPO3)4] (1) and [HCHPA]2[Zn3(HPO3)4] (2), have been synthesized under hydrothermal conditions, where CHA = cyclohexylamine and CHPA = cycloheptylamine. Both compounds are isostructural and exhibit a similar three-dimensional 3, 4-connected framework constructed by strictly alternating ZnO4 tetrahedra and HPO32− pseudopyramids. The occurrence of extra-large tubular channels constructed by the concatenation of 24- and 30-ring windows along the [001] direction in the two structures is very unusual in known extra-large micropore materials. Crystal data: 1, rhombohedral, R-3, a = 32.9618(5) Å, c = 13.2818(3) Å, V = 12497.1(4) Å3, Z = 18, R1 = 0.0445, wR2 = 0.1068; 2, rhombohedral, R-3, a = 33.2184(4) Å, c = 13.1697(6) Å, V = 12585.3(6) Å3, Z = 18, R1 = 0.0401, wR2 = 0.0974.

Three-Dimensional Open-Framework Zinc Phosphite: Synthesis and Characterization

Generally, open-framework metal phosphites like phosphates, are synthesized under hydrothermal or solvothermal conditions in the presence of organic amines, which may act as structure-directing agent or template to avoid the formation of dense phase, but few of them has been successfully prepared at room temperature which seems to be difficult to synthesize these compounds. In this work, at room temperature, employing n-propylamine as a template, a three-dimensional zinc phosphite (C3H10N) 2·[Zn3(HPO3)4] has been prepared and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The compound crystallizes in the orthorhombic space group Pccn, with cell parameters, a = 9.839(3) Å, b = 23.356(8) Å, c = 8.970(3) Å, V = 2050.2(8) nm3 and Z = 4.

Three-Dimensional Open-Framework Zinc Phosphite: Synthesis and Characterization

Generally, open-framework metal phosphites like phosphates, are synthesized under hydrothermal or solvothermal conditions in the presence of organic amines, which may act as structure-directing agent or template to avoid the formation of dense phase, but few of them has been successfully prepared at room temperature which seems to be difficult to synthesize these compounds. In this work, at room temperature, employing n-propylamine as a template, a three-dimensional zinc phosphite (C3H10N) 2·[Zn3(HPO3)4] has been prepared and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The compound crystallizes in the orthorhombic space group Pccn, with cell parameters, a = 9.839(3) Å, b = 23.356(8) Å, c = 8.970(3) Å, V = 2050.2(8) nm3 and Z = 4.

Synthesis and characterization of a new open-framework zinc phosphite (4,4′-(C5H4N)2(CH2)3)·[Zn3(HPO3)4

Employing 4,4′-trimethylenedipyridine as a template, a new two-dimensional zinc phosphite (4,4′-(C5H4N)2(CH2)3)· [Zn3(HPO3)4] has been prepared at room temperature and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The compound crystallizes in the monoclinic space group P21/c, with cell parameters, a = 9.3309(19) A, b = 14.798(3) A, c = 33.637(7) A, β = 91.11(3)°, V = 4643.8(16) nm3 and Z = 4. The connectivity of the ZnO4 tetrahedra and HPO3 pseudo pyramids results in infinite corner-sharing 4-membered ring chains as second building units which are further linked by Zn-O-P bonds to form a 2-D layer that with interesting 8-membered ring channels along the [100] direction. The diprotonated 4,4′-trimethylenedipyridine molecules sit in the middle of the layers along the [100] direction and interact with the framework via hydrogen bonds.

ChemInform Abstract: Synthesis and Characterization of Three Open‐Framework Zinc Phosphites with (3,4)‐Connected Frameworks.

AbstractThe crystal structures of the new open‐framework zinc phosphite compounds (II), (IV), and (V) are determined by single crystal XRD.

ChemInform Abstract: Flux Synthesis of Two New Organically Templated Zinc Phosphites with Different 3,4‐Connected Frameworks.

AbstractCompounds (II) are prepared by a phosphorus acid flux method without the addition of water as solvent.

Synthesis and characterization of three open-framework zinc phosphites with (3,4)-connected frameworks

By using different monoamines as the structure-directing agents, three new open-framework zinc phosphite compounds, [C 4H 10ON] 2·[Zn 3(HPO 3) 4] ( 1), [CH 3CH 2NH 3] 2·[Zn 3(HPO 3) 4] ( 2) and [H 2N(CH 3) 2] 2·[Zn 3(HPO 3) 4] ( 3), have been synthesized under hydro/solvothermal conditions. The three compounds have different (3,4)-connected frameworks constructed from strictly alternating ZnO 4 tetrahedra and HPO 3 pseudo pyramids. The presence of 12-ring channels in their structures is noteworthy. The removal of organic cations in the free voids of compound 1 by an ion-exchange process will make the structure collapse.

Flux synthesis of two new organically templated zinc phosphites with different 3,4-connected frameworks

Two new organically templated zinc phosphites, H 2depda·Zn 3(HPO 3) 4 ( 1) and H 2dmpda·Zn 3(HPO 3) 4 ( 2), have been synthesized under flux conditions, where depda = N, N-diethyl-1,3-propanediamine and dmpda = N, N-dimethyl-1,3-propanediamine. The two compounds have different (3,4)-connected inorganic frameworks constructed by strictly alternating ZnO 4 tetrahedra and HPO 3 pseudo pyramids. The presence of large 12-ring channels in the two open-framework structures is noteworthy.

Natural abundance solid-state 67Zn NMR characterization of microporous zinc phosphites and zinc phosphates at ultrahigh magnetic field

Zinc-phosphite and -phosphate based microporous materials are crystalline open framework materials with potential industrial applications. Although (31)P MAS NMR has been used for characterization of these materials, the local environments around zinc centres have never been directly probed by solid-state NMR due to the many unfavourable NMR characteristics of (67)Zn. In this work, we have characterized the local structure around the Zn centres in several representative microporous zinc phosphites and zinc phosphates by acquiring natural abundance (67)Zn solid-state NMR spectra at ultrahigh magnetic field of 21.1 T. The observed line-shapes are mainly determined by the second order quadrupolar interaction. The NMR tensor parameters were extracted from the spectra and are related to the local geometry around the Zn centre. Computational study of the electric field gradient (EFG) tensor at Zn was performed using hybrid density functional theory (DFT) calculations at B3LYP level of theory on model clusters. The calculations using Projector Augmented-Wave (PAW) method were also carried out with the CASTEP code wherever it was possible. The work has shown that it is possible to study Zn environments in porous materials which often have very low Zn concentration by natural abundance (67)Zn SSNMR at very high magnetic fields.

Synthesis, characterization, and catalytic behavior of two open-framework zinc phosphites with 2D and 3D structures

Abstract Two new zincophosphites are obtained via a hydrothermal process. Single crystal data indicate that 1 has a two dimensional motif with the organic amine template embedded between the layers, while 2 has a three-dimensional structure with the organic amine template enclosed into the cavities. Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate is carried out with these two complexes as support in ethanol at 333 K respectively. Experimental results indicate that only 1 is efficient for the catalysis. The catalytic ability depends on their structural characters.

A novel three-dimensional pillared-layer hybrid zinc phosphite featuring double-helical channels

A new zinc phosphite (C2H8N2)0.5(HPO3)Zn has been hydrothermally synthesized from a mixture of ZnO, H3PO3, 4,4’-bipyridine, ethylenediamine, and H2O. Single-crystal X-ray diffraction analysis reveals that the Zn ions are first interconnected by HPO32- ligands to produce a neutrally infinite two-dimensional inorganic layer with four- and eight-membered rings, which is further used as the second building units and helically pillared by bridging ethylenediamine molecules to form the scarcely reported three-dimensional pillared-layer hybrid zinc phosphite with double-helical channels due to the flexibility of the ethylenediamine ligands.

Flux synthesis of two new open-framework zinc phosphites with 16-ring channels

Two new three-dimensional open-framework zinc phosphites, (H 2aep) 2·Zn 6(HPO 3) 8 ( 1) and H 3taea·Zn 3(HPO 3) 4.5 ( 2) have been synthesized by the H 3PO 3 flux method, where aep = 1-(2-aminoethyl)piperazine and taea = tris(2-aminoethyl)amine. Compound 1 has a 3,4-connected framework with (4,6,8) sheets connected by corner-sharing 4-ring chains. Compound 2 has 3-connected sheets built from quintuple-fused 4-rings, which are further linked by HPO 3 units to form the three-dimensional structure. The presence of large 16-ring channels in the two structures is noteworthy. Crystal data: 1, monoclinic, P2 1/c, a = 18.8613(7) Å, b = 9.0856(5) Å, c = 24.9485(8) Å, β = 107.211(6)°, V = 4083.9(3) Å 3, Z = 4, R 1 = 0.0457, wR 2 = 0.1050; 2, monoclinic, C2/c, a = 28.911(2) Å, b = 8.302(3) Å, c = 19.513(3) Å, β = 103.715(16)°, V = 4549.8(17) Å 3, Z = 4, R 1 = 0.0428, wR 2 = 0.1165.

ChemInform Abstract: Flux Synthesis of (3,4)‐Connected Zinc Phosphites with Different Framework Topologies.

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Ionothermal synthesis of a new open-framework zinc phosphite NIS-3 with low framework density

The first ionothermal case of open-framework metal phosphite, Zn3(HPO3)4·2C6H11N2, denoted NIS-3, was prepared using 1-ethyl-3-methyl imidazolium bromide as solvent and template.