QD-2: a novel open-framework aluminoborate with intersecting three-dimensional helical channels

A novel open-framework aluminoborate, [CH3NH2(CH2)3NH ]-[AlB5O10] (QD-2), has been synthesized under hydrothermal conditions and characterized by IR, elemental analysis, thermogravimetric analysis, and powder and single-crystal X-ray diffractions. The compound crystallizes in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), a = 9.4352(4) A, b = 10.2972(2) A, c = 13.7511(5) A, V = 1336.0(8) A3, and Z = 4. Its structure consists of AlO4 tetrahedra and B5O10 clusters, which are interconnected to form the first example of a three-dimensional aluminoborate with intersecting helical channels.     

ITQ-15: the first ultralarge pore zeolite with a bi-directional pore system formed by intersecting 14- and 12-ring channels, and its catalytic implications

The pore topology of ITQ-15 zeolite consists of an ultra-large 14-ring channel that is intersected perpendicularly by a 12-ring pore; acid sites have been introduced in its framework and this unique structure shows advantages over unidirectional ultralarge pore zeolites for diffusing and reacting large molecules.     

Synthesis and characterization of a new organically templated open-framework beryllium phosphite with 3, 4-connected networks

Employing diethylenetriamine (=dien) as a structure-directing agent, a new open-framework beryllium phosphite H₂dien·Be₃(HPO₃)₄ (1), has been synthesized hydrothermally and structurally characterized by single crystal X-ray diffraction. The structure of 1 features a (3, 4)-connected framework with 8- and 12-ring channels, which is constructed from strictly alternating BeO₄ tetrahedra and HPO₃²⁻ pseudopyramids. The 3-D framework possesses a pcu topology when the heptameric [Be₃(HPO₃)₄] clusters are regarded as 6-connected secondary building units. Crystal data: 1, monoclinic, C2/c (no. 15), a = 8.7350(3) Å, b = 15.1704(6) Å, c = 13.0851(4) Å, β = 101.223(5)°, V = 1700.79(10) Å³, Z = 4, R₁ = 0.0625, wR₂ = 0.1692.     

Synthesis,structure and characterization of five new organically templated metal sulfates with 2‐aminopyridinium

The chemistry of organically templated metal sulfates has attracted interest from the materials science community and the development of synthetic strategies for the preparation of organic–inorganic hybrid materials with novel structures and special properties is of current interest. Sulfur–oxygen–metal linkages provide the possibility of using sulfate tetrahedra as building units to form new solid‐state materials. A series of novel organically templated metal sulfates of 2‐aminopyridinium (2ap) with aluminium(III), cobalt(II), magnesium(II), nickel(II) and zinc(II) were obtained from the respective aqueous solutions and studied by single‐crystal X‐ray diffraction. The compounds crystallize in centrosymmetric triclinic unit cells in three structure types: type 1 for 2‐aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate, (C₅H₇N₂)[Al(H₂O)₆](SO₄)₂·4H₂O, (I); type 2 for bis(2‐aminopyridinium) tris[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate, (C₅H₇N₂)₂[Co(H₂O)₆]₃(SO₄)₄·2H₂O, (II), and bis(2‐aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis(sulfate) dihydrate, (C₅H₇N₂)₂[Mg(H₂O)₆]₃(SO₄)₄·2H₂O, (III); and type 3 for bis(2‐aminopyridinium) hexaaquanickel(II) bis(sulfate), (C₅H₇N₂)₂[Ni(H₂O)₆](SO₄)₂, (IV), and bis(2‐aminopyridinium) hexaaquazinc(II) bis(sulfate), (C₅H₇N₂)₂[Zn(H₂O)₆](SO₄)₂, (V). The templating role of the 2ap cation in all of the reported crystalline substances is governed by the formation of characteristic charge‐assisted hydrogen‐bonded pairs with sulfate anions and the presence of π–π interactions between the cations. Additionally, both coordinated and uncoordinated water molecules are involved in hydrogen‐bond formation. As a consequence, extensive three‐dimensional hydrogen‐bonding patterns are formed in the reported crystal structures.     

Synthesis and Structure of KBGe2O6: the first chiral zeotype borogermanate with 7-ring channels

Among the known zeolite topologies, odd rings are rare with the exception of 5-ring. We report here the hydrothermal synthesis and structural characterization of a novel compound, KBGe(2)O(6), the first germanate-based zeotype material with 7-ring channels. It crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), a = 4.8037(3) A, b = 10.2063(7) A, c = 10.7402(10) A, V = 526.57(5) A(3), Z = 3. The framework topology of this compound is previous unknown with the vertex symbol 4.6.4.6.6.7(2)(vertex1), 4.6.4.6.6.7(2)(vertex2), and 6.6.6.6.6(2) x 7(2)(vertex3). It is worth noting that the structure of the compound is chiral containing helices condensed from GeO(4) tetrahedra, which arrange around 2(1) screw axes. Furthermore, the K(+) ions within the channels are mobile and can be partially ion-exchanged with Na(+) at room temperature.     

Synthesis and characterization of a novel organically templated open framework zirconogermanate with three- and seven-membered rings

A new organically templated microporous zirconogermanate, (C(2)H(10)N(2))H(2)O[ZrGe(3)O(9)] (denoted as FDZG-3), with a low framework density of 13.6 T/1000 A(3), has been solvo/hydrothermally synthesized by using ZrO(NO(3))(2).2H(2)O as a zirconium source and triethylenetetramine (TETA) as a structure direct agent. This compound was characterized by means of single-crystal X-ray diffraction analysis, thermogravimetrical analysis, and IR and UV-vis spectra. Its three-dimensional (3D) framework is built up by 1D sinusoidal germanate chains cross-linked by ZrO(6) octahedra, which forms a network containing three- and seven-membered rings (MRs). Four intersecting 7-MR channels can be observed along the b axis, c axis, [110], and [-110] directions, respectively. Charge-balancing (C(2)H(10)N(2))(2+) and extraframework water molecules are encapsulated within 7-MR channels and form hydrogen bonds with framework oxygen atoms. Crystal data for FDZG-3: M = 533.13, monoclinic, space group Cc (No.9), a = 11.299(3) A, b = 7.7649(19) A, c = 13.835(3) A, beta = 104.826(3) degrees, V = 1173.4(5) A(3), Z = 4, R1 = 0.0263, wR2 = 0.0529.     

Syntheses and crystal structures of the first organically templated metal tellurites

The first organically templated vanadium tellurites, [H₂en][(VO₂)(TeO₃)]₂·H₂O (1, en=ethylenediamine) and [H₂pip][(VO₂)(TeO₃)]₂ (2, pip=piperazine) have been synthesized by hydrothermal reactions and structurally characterized. Both compounds feature a [(VO₂)(TeO₃)]⁻ anionic layer containing V₂Te₂ four-member rings and V₄Te₄ eight member rings. The vanadium (V) atom is five coordinated by three tellurite oxygens and two terminal oxygen atoms in a distorted trigonal bipyramidal geometry. The interconnection of the VO₅ polyhedra by bridging tellurite groups leads to a 2D corrugated anionic inorganic layer. The doubly protonated template cations and the lattice water molecules in 1 are located at the interlayer space and are involved in hydrogen bonding. The doubly protonated template cation in 2 is not involved in hydrogen bonding with the anionic inorganic layer.     

Synthesis and characterization of the first trimetallic nitride templated pyrrolidino endohedral metallofullerenes

New pyrrolidino derivatives of both diamagnetic and paramagnetic trimetallic nitride templated endohedral metallofullerenes were synthesized by the Prato reaction, isolated and characterized by means of MALDI-TOF MS, NMR and UV-vis spectroscopies.     

Synthesis and characterization of a new open-framework fluorinated gallium phosphite with three-dimensional intersecting channels

(C₄N₂H₁₂)[Ga₂F₃(HPO₃)₂(H₂PO₃)] 1 is a new open-framework fluorinated gallium phosphite obtained by mild hydrothermal synthesis using piperazine as template agent and characterized by single crystal X-ray diffraction (XRD), powder XRD, infra-red spectroscopy, inductively coupled plasma, thermogravimetric and elemental analyses. The three-dimensional (3D) anionic framework of compound 1 is constructed from two distinct motifs, a 1D tancoite chain and a single 4-ring (S4R) unit, which contains four intersecting channels running throughout the structure as 8, 12-member rings channels along to the a-axis and 12-member ring channels along the b- and c-axis, respectively. The well-ordered, diprotonated piperazine cations occupy all the channels, and interact with the fluorinated gallium-phosphite framework by strong hydrogen bonds.     

Synthesis and characterization of the first organically templated metal oxalatophosphonate: (C3H12N2)0.5[Ga3(C2O4)(CH3PO3)4].0.5H2O

The first organically templated gallium oxalatophosphonate has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The structure consists of GaO(6) octahedra and GaO(4) tetrahedra connected by methylphosphonate and bis-bidentate oxalate anions to form anionic sheets in the ab plane with the charge-compensating propylenediammonium cations and water molecules between the sheets. The methyl groups of the phosphonate ligands extend from both sides of the layers into the interlamellar region. Crystal data: monoclinic, space group P2(1)/n (No. 14), a = 8.8514(4) A, b = 16.3030(7) A, c = 15.0816(7) A, beta = 97.539(1) degrees, and Z = 4.     

Hydrothermal synthesis and characterization of two organically templated cadmium borophosphates with novel structures

Two organically templated cadmium borophosphates, (C(4)H(16)N(3))[CdClB(2)P(3)O(12)(OH)] (1) and (C(2)H(10)N(2))[CdB(2)P(3)O(12)(OH)] (2), were synthesized hydrothermally in the presence of structure-directing amines. Compound 1 has a complex layered structure (orthorhombic, Pbca (No. 61); a = 9.470(2), b = 12.307(3), c = 27.311(6) A; V = 3183 (1) A(3); Z = 8) with a 9MR channel system, while compound 2 (orthorhombic, Pbca (No. 61); a = 9.286(3), b = 12.459(3), c = 21.626(6) A; V = 2502(1) A(3); Z = 8) presents a 3-dimensional open framework structure of different types of intersecting channels. It is worth noting that both the Cl(-) anions and the organic templates play important and interesting roles in the formation of the structures.     

GeB4O9 x H2en: an organically templated borogermanate with large 12-ring channels built by B4O9 polyanions and GeO4 units: host-guest symmetry and charge matching in triangular-tetrahedral frameworks

A new borogermanate open-framework, FJ-18, with intersecting 12-/8-, 9-, and 9-ring channels in multidimensions was synthesized by using an organic diamine as structure-directing agent (SDA). X-ray diffraction showed that its structure is constructed by flexible connection of strictly alternate B(4)O(9) clusters (with fictitious tetrahedral geometry) and GeO(4) tetrahedra to form a zeotype framework with the CrB(4) topology. The topology and structural relations between FJ-18 and FJ-16, a known borogermanate based on the linkage of B(4)O(9) clusters and GeO(4) units, are described in detail. Different guest SDAs can, by means of their shape, size, and charge, directly influence the structure of the host framework, and the origin of these phenomena can be attributed to fundamental parameters such as host-guest symmetry and charge matching through H-bonding interactions, the concept of which has for the first time been extended to tetrahedral-triangular frameworks. This result is a part of our ongoing work aimed at making new large-pore materials constructed from B-O polyanions and Ge-O cluster units.     

Convergent and Stereoselective Synthesis of Sarcophytol-Q Precursor: (11S)-3,7,11,15-Tetramethyl-11-hydroxy-14-oxo-3E,7E,12E-hexadecatrienal

A chiral precursor of sarcophytol-Q, (11S)-3,7,11,15-tetramethyl-11-hydroxy-14-oxo-3E,7E,12E-hexadecatrienal, was synthesized in a convergent and stereoselective manner starting from geraniol and 4-hydroxy-2-butanone in nine steps. The key steps were asymmetric Sharpless epoxidation, base-induced dehydrohalogenation rearrangement of chiral epoxy chloride 5 and the phase transfer catalytic coupling reaction of allylic phenyl sulfone 4 with chiral allylic chloride 3 .     

Synthesis, characterization, and catalytic performance of Cr-incorporated aluminoborate octahedral molecular sieves

A series of Cr-incorporated PKU-1 molecular sieves (Cr-PKU-1) were synthesized by using boric acid as a flux, and the physicochemical properties were characterized by XRD, ICP, SEM, XPS, UV-vis, and NH3-TPD methods. The morphology of Cr-PKU-1 is a needlelike hexagonal prism with uniform size of about 2 microm in diameter and 20-50 microm in length. XRD and UV-vis provide direct evidence that Cr ions have been successfully incorporated into the framework of PKU-1. NH3-TPD shows a dramatic increase of acidic sites in the Cr-PKU-1 in comparison with PKU-1, indicating that the Cr incorporation can significantly modify the acidity of the compound. In addition, the incorporated Cr ions may act as redox centers, thus catalytic performance of Cr-PKU-1 molecular sieve was investigated by the selective oxidation of styrene under mild reaction conditions.     

Synthesis and structure of QD-6: a novel aluminoborate constructed from unprecedented [B@Al6O24] and polyborate clusters

A novel aluminoborate (NH(4))(6)[C(5)NH(12)](6)[Al(12)B(65)O(105)(OH)(33)]·(H(2)O)(15) (QD-6), has been synthesized under mild hydrothermal conditions and characterized by IR, elemental analysis, TGA, powder and single-crystal X-ray diffractions. This compound crystallizes in the rhombohedral space group R3 (No. 148) with the lattice constants a = 23.7421(2) ?, c = 24.7699(3) ?, V = 12091.9(2) ?(3), and Z = 3. QD-6 consists of two unprecedented aluminoborate clusters, [Al(6)B(34)O(54)(OH)(18)](6-) and [Al(6)B(31)O(51)(OH)(15)](6-), which are built from the same hexagon-like [B@Al(6)O(24)] clusters and [B(11)O(17)(OH)(6)] or [B(10)O(16)(OH)(5)] polyborates.     

MCuB7O12.nH2O (M = Na, K ): a new copper borate with 14-ring channels

The title compounds, which were synthesized in boric acid flux under mild conditions (493 K), contain a 14-member ring borate framework consisting of octahedral (CuO6), tetrahedral (BO4) and triangular (BO3) units.     

Synthesis of a new zeolite structure ITQ-24, with intersecting 10- and 12-membered ring pores

A new 10- and 12-membered ring zeolite, named ITQ-24, has been synthesized, and its structure has been solved. It has been found that this zeolite structure is topologically identical to that proposed for the hypothetical polymorph C of the SSZ-33/SSZ-26/CIT-1 family. This new zeolite has been achieved by using a rational approach of introducing Ge in the framework that has a directing effect toward zeolite structures with double-four-membered rings as secondary building units. Notoriously, active catalytic centers, such as Ti and Al, have been incorporated into this new zeolite, demonstrating that it is catalytically active for alkylation of aromatics.     

Synthesis of (+)-2R,3R,11R,12R- and (−)-2S,3S,11S,12S-tetraphenyl-18-crown-6

The synthesis of the title crown ethers starting from optically active hydrobenzoins is described. R(+)-1,in CDCl₃ ,preferentially extracts R(+)-phenylglycine methyl ester hydroperchlorate from an aqueous solution of the racemate with a chiral recognition factor of 1.5 as shown by nmr measurements.     

|(C4NH12)4|[M4Al12P16O64] (M = Co, Zn): new heteroatom-containing aluminophosphate molecular sieves with two intersecting 8-ring channels

Two novel heteroatom-containing aluminophosphate molecular sieves, |(C(4)NH(12))(4)|[M(4)Al(12)P(16)O(64)] (denoted MAPO-CJ69, M = Co and Zn), have been solvothermally synthesized using diethylamine as the structure-directing agent. The framework of MAPO-CJ69 exhibits a new zeolite topology which is constructed by strict alternation of metal-centered (Al/M)O(4) tetrahedra and PO(4) tetrahedra to form a three-dimensional anionic [M(4)Al(12)(PO(4))(16)](4-) framework. The structure contains two intersecting 8-ring channels along the [010] and [001] directions, and the protonated diethylamine cations reside in the 8-ring channels to achieve charge neutrality. The structure of MAPO-CJ69 is composed of the 4-4- secondary building unit (SBU), which has been found in some known zeolites, such as AFR, SFO, ZON, OWE, etc. The structural relationships between these zeolites have been discussed.