Re. 19,632 7/1935 Arnold ................................ 260/127 1,926,691 9/1933 Swallen et al. ..................... 260/127 1,992,935 3/1935 Arnold ................................ 260/127 2,349,222 5/1944 Goshorn ............................. 260/585 2,394,515 2/1946 Goshorn ............................. 260/583 2,394,516 2/1946 Goshorn ............................. 260/583 2,456,599 12/1948 Smith .................................. 260/585 3,278,598 10/1966 Markiewitz ......................... 260/563 3,384,667 5/1968 Hamilton ............................ 260/585 3,387,032 6/1968 Leonard .............................. 260/585 3,904,738 9/1975 Robson ............................... 423/328 4,082,805 4/1978 Kaeding .............................. 260/585 11) Patent Number: 4,806,689

While extensive commercial success has been achieved through the use of organic molecules in the synthesis of aluminosilicate zeolites, the synthesis of the germanium-based zeolite structures using organic structure-directing agents is a largely unexplored area. Here we report a novel class of germanate zeolite structures prepared with inorganic cations or organic amines as structure-directing agents. These new materials possess five 4-connected S-dimensional topologies with large (12-ring), medium (10-ring), small (8-ring), or ultrasmall (6-ring) pores. They have a variety of chemical compositions such as various Ge to Ga (or Al) ratios and exhibit interesting structural features such as helical chains and odd-membered rings. UCSB-15GaCe and UCSB-15AlGe are the first germanate-based structures with 5-rings. UCSB-7 refers to a collection of isostructural, large-pore zeolite-like structures constructed by the cross-linking of helical ribbons. UCSB-3GaGe is the only known T3+/T4+ (T refers to tetrahedral atoms) based zeolite structure with the net 38 topology. This structure is unusual because of its very high framework charge density unsurpassed by other amine-directed zeolite structures. GaGe-SOD2 and AlGe-SOD2 (sodalite analogues) have an unusually low framework symmetry for a sodalite structure. The cubic GaGe-SOD1 (or AlGe-SOD1) and the triclinic GaGe-SOD2 (or AlGe-SOD2) are ideal examples of the compositional and structural control of the inorganic framework by structure-directing amines. GaGe-ANA1 and GaGe-ANA2, two gallogermanate analcime analogues, are noncentrosymmetric, unlike many other analcime structures.

The increasing demand for enantiomerically pure chemicals has stimulated extensive research into the preparation of heterogeneous chiral catalysts or separation media that combine both shape selectivity and enantioselectivity1. Helical pores in inorganic materials might be able to perform such functions, but their occurrence is rare1. Attempts have been reported to synthesize a specific enantiomorph of the chiral zeolite beta2, and chiral metal complexes have been used to assemble inorganic precursors into chiral frameworks3,4. Materials with a fully three-dimensional array of helical structural units are particularly rare, because helical structures (such as quartz) are commonly generated by a uni-dimensional symmetry element acting on an achiral structural subunit5,6. Here we report on a family of zeolite-type materials (which we call UCSB-7) that possess two independent sets of three-dimensional crosslinked helical pores, separated by a gyroid periodic minimal surface13. We have synthesized the UCSB-7 framework for various compositions (zinc and beryllium arsenates, gallium germanate) using either inorganic cations or amines as structure-directing agents. The helical-ribbon motif that we identify might be exploited more widely for developing useful chiral solid-state structures.

Crystals of α-CsTi3P5O19, the low temperature phase, and β-CsTi3P5O19, the high temperature phase, have been obtained by flux growth methods and structurally characterized by single crystal X-ray diffraction techniques. Crystal data: α-CsTi3P5O19, monoclinic, Cm , a = 9.309(2) Å, b = 14.081(3) Å, c = 6.314(1) Å, β = 105.82(3)°, V = 796.3 Å3Z = 2, R = 0.027 for 928 unique reflections; β-CsTi3P5O19, monoclinic, C 2/c, a = 10.987(1) Å, b = 16.588(1) Å, c = 8.7618(8) Å, β = 100.09(1)°, V = 1572.2 Å3, Z = 4, R = 0.038 for 1678 unique reflections. The two polymorphs have different three-dimensional networks of vertex-sharing octahedra and tetraheda. The framework of the α-phase consists of dimers of corner-sharing TiO6 octahedra and discrete TiO6 octahedra joined through PO4 tetrahedra and P2O7 groups by corner-sharing. The β-phase is built up from discrete TiO6 octahedra, PO4 tetrahedra, and P2O7 groups. The structural formulas are CsTi(Ti2O)(PO4)(P2O7)2 and CsTi3(PO4)3(P2O7) for the α- and β-phases, respectively. Both frameworks have tunnels where the cesium cations are located. The cesium cations in the β-phase are disordered.

The sodalite cage containing only an electron as a nonframework ''anion' is well adapted for the study of solvated ''electride'' Wigner lattices and quantitative mapping of the intra- and intercage electronic potential surfaces. In this paper we report the direct synthesis of anion free cage structures of the form Na3[](ABO4)3.nH2O (A; B = Al, Ga; Si, Ge) as possible precursors for sodalite electride synthesis. A novel, low-temperature sodalite dehydroxylation method is presented for the preparation of Na3[](AlSiO4)3.4H2O from Na4[OH](AlSiO4)3.1.72H2O. Results from a neutron diffraction study of Na3(ZnAsO4)3.4H2O give evidence of hydrogen bonding between the framework oxygen atoms and the beta-cage substructure and aid in explanation of analog unit cell trends. All of the investigated sodalites have an ordered array of their framework tetrahedral cations and crystallize in the cubic space group P43nBAR, Z = 2. Two of these new sodalites were characterized by single-crystal X-ray diffraction. Na3(AlGeO4)3.4H2O, with a = 8.965(1) angstrom, d(Al-O) = 1.746(4) angstrom, d(Ge-O) = 1.758(4) angstrom, and THETA(Al-O-Ge) = 129.6(2)degrees, has beta-cages which contain a defect-''cubane''-like Na3.4H2O array. Final disagreement factors: R = 1.93% and R(w) = 2.19% for 208 observed reflections [I > 3sigma(I)]. Na3(GaGeO4)3-4H2O, with a = 9.0033(7) angstrom, d(Ga-O) = 1.839(3) angstrom, d(Ge-O) = 1.745(3) angstrom, and THETA(Ga-O-Ge) = 125.3(2)degrees, has the same beta-cage contents. Final disagreement factors of R = 1.00% and R(w) = 1.29% were obtained for 183 observed reflections [I > 3sigma(I)]. The structure of Na3-[(GaSiO4)3].4H2O was determined by Rietveld refinement of room-temperature X-ray powder diffraction data, with a = 8.8614(2) angstrom, d(Ga-O) = 1.847(4) angstrom, d(Si-O) = 1.580(3) angstrom, THETA(Ga-O-Si) = 131.9(3)degrees, and the same beta-cage contents. Final disagreement factors of R(p) = 10.07% and R(wp) = 13.75% for 4099 data were obtained. The structure of Na3(ZnASO4)3.4H2O was determined from low-temperature continuous-wavelength neutron powder diffraction data, with a = 9.0276(7) angstrom, d(Zn-O) = 1.974(4) angstrom, d(As-O) = 1.689(4) angstrom, THETA(Zn-O-As) = 121.1(3)degrees, and the same beta-cage contents, with evidence of hydrogen bonding between cubane and framework atoms. Final disagreement factors of R(p) = 4.26% and R(wp) = 5.52% for 3268 data were obtained. These isomorphs are compared with other Na3[](ABO4)3.4H2O types of sodalite structures in terms of geometrical trends in 6-ring topologies and cation and water molecule sitings. Further structural information is obtained through presented spectral, thermogravimetric, and physical data.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStructural and Chemical Investigations of Na3(ABO4)3.cntdot.4H2O-Type Sodalite PhasesTina M. Nenoff, William T. A. Harrison, Thurman E. Gier, Nancy L. Keder, Charlotte M. Zaremba, Vojislav I. Srdanov, Jaqueline M. Nicol, and Galen D. StuckyCite this: Inorg. Chem. 1994, 33, 11, 2472–2480Publication Date (Print):May 1, 1994Publication History Published online1 May 2002Published inissue 1 May 1994https://doi.org/10.1021/ic00089a026Request reuse permissionsArticle Views183Altmetric-Citations43LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Two new, noncentrosymmetric, rubidium titanium phosphate phases have been synthesized by hydrothermal and flux methods and structurally characterized by single crystal X-ray diffraction methods. Rb2Ti3O2(PO4)2(HPO4)2 (Rb2Ti3P4) consists of a three-dimensional framework of vertex-sharing TiO6, PO4, and HPO4 polyhedra interconnected via Ti-O-Ti and Ti-O-P bonds, surrounding large, one-dimensional channels occupied by eight-coordinate \"guest\" Rb+ cations: these channels propagate along the a-crystallographic direction. The framework includes [Ti3O16] units built up from three adjacent TiO6 octahedra sharing trans-O-Ti-O links, crosslinked by the (hydrogen)phosphate groups. Rb3Ti3O (P2O7)(PO4)3 (Rb3Ti3P5) is built up from a network of TiO6 and PO4 groups, linked via Ti-O-Ti, Ti-O-P, and P-O-P bonds, enclosing channels occupied by the guest rubidium cations. The structural motif of the framework includes isolated TiO6 and [Ti2O11] groups, interconnected by (pyro)phosphate groups. The Rb+ cations occupying the one-dimensional channels are eighffold coordinate by oxygen atoms. Rb3Ti3O(P2O7)(PO4)3 (2 linked octahedra) and RbaTi3O2(PO4)2(HPO4)2(3 linked octahedra) are considered in relation to the nonlinear optical materials KTiOPO4 (KTP) and RbTiOPO4 (RbTP) which contain infinite -O-Ti-O-Ti-O-chains. The typical short, \"titanyl\" Ti[]O bond found in KTP and RbTP is barely apparent in Rb2Ti3O2(PO4)2(HPO4)2 and Rb3 Ti3O(P2O7)(PO4)3, and the poor nonlinear response of the title compounds is discussed in relation to the extended Ti/O chain structure in RbTP. Crystal data: Rb2Ti3P4O18H2, Mr = 728.5, monoclinic, P21, a = 5.1851(4) A, b = 16.770(2) A, c = 8.4939(6) A β = 90.940(3) °, V = 738.48 A3, Z = 2. Final residuals of R = 4,24% and Rw = 4.40% were obtained for 2331 unique reflections with I \u003e 3σ(I). Rb3Ti3P5O20, Mr = 874.96, orthorhombic, Pca21, a = 18.280(1) A, b = 6.295(1) A, c = 14.773(1) A, V = 1700.0 A3, Z = 4, R = 4.00%, and Rw = 3.70% for 1498 unique reflections with I \u003e 3σ(I).

The hydrothermal syntheses and X-ray single-crystal structures of Be2AsO4OH.4H2O and Na2ZnPO4OH.7H2O, two phases which contain 3-ring groupings of tetrahedra as part of 1-dimensional chains Of MXO4 (M = Zn, Be; X = P, As) groups, are reported. MAS NMR and TGA data are reported for these phases, and the structures of these two materials are briefly compared with those of some other known extended tetrahedral species. Crystal data for Be2AsO4OH.4H2O (BAO): M(r) = 246.01; monoclinic, space group P2(1)/a, with a = 7.2349(8) angstrom, b = 12.686(2) angstrom, c = 8.6546(9) angstrom, and beta = 98.439(3)degrees; Z = 4. Final residuals of R = 4.49% and R(w) = 4.79% were obtained for 2333 observed reflections [I > 3sigma(I)]. BAO contains 1-dimensional stacks of interconnected BeO4 and AsO4 tetrahedra, including alternating 4-rings and 3-rings, the latter ring system containing Be-(OH)-Be bonds. The tetrahedral columns are held together by water molecules, via a network of H-bonds. Crystal data for Na2ZnPO4-OH.7H2O (NZPO): M(r) = 349.43; monoclinic, space group P2(1)/a, with a = 6.4212(6) angstrom, b = 21.612(2) angstrom, c = 8.6813(6) angstrom, and beta = 109.899(3)degrees; Z = 4. R = 5.85% and R(w) = 5.61% for 2654 observed reflections [I > 3sigma(I)]. NZPO also contains 1-dimensional tetrahedral stacks (ZnO4 and PO4 moieties) made up only of 3-rings which include Zn-(OH)-Zn connections. Adjacent stacks are interconnected via a complex arrangement of sodium cations and water molecules.

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ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTetrahedral-atom 3-ring groupings in 1-dimensional inorganic chains: beryllium arsenate hydroxide hydrate (Be2AsO4OH.cntdot.4H2O) and sodium zinc hydroxide phosphate hydrate (Na2ZnPO4OH.cntdot.7H2O)William T. A. Harrison, Tina M. Nenoff, Thurman E. Gier, and Galen D. StuckyCite this: Inorg. Chem. 1993, 32, 11, 2437–2441Publication Date (Print):May 1, 1993Publication History Published online1 May 2002Published inissue 1 May 1993https://pubs.acs.org/doi/10.1021/ic00063a039https://doi.org/10.1021/ic00063a039research-articleACS PublicationsRequest reuse permissionsArticle Views389Altmetric-Citations98LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

: The synthesis of the solid solution series Ga(x)Zn(8-x)(BO2)12P(x) Se(2-x) (x = 0, 0.5, 1, 2) is reported and the local and average long-range structures are discussed based on x-ray diffraction data, UV/visible spectroscopic measurements and a variety of field-dependent static and magic angle spinning and solid state NMR experiments. Inclusion of GaP within the borate sodalite analogue results in the formation of an isolated 31p-69,71 Ga dipolar spin pair that exhibits resolved J-coupling in the 31P MAS NMR spectra. Theoretical analysis reveals that there are four different intracage structures distributed in small domains throughout the crystallographically single phase materials and these are identified as (Zn4Se)(6+), (GaZn3 P)(6+), (Zn4 P)(5+) and, by inference, (Ga2Zn2P)(7+).

: Two new titanium pyroarsenate phases, alpha-TiAS2O7 and beta-TiAS2O7, have been prepared by high temperature hydrothermal methods and characterized by single crystal x-ray diffraction techniques. Both structures are based on different three-dimensional networks of vertex-sharing TiO6 octahedra and AsO4 tetrahedra. The TiO6 groups show little distortion from regular octahedral geometry, and the arsenate anions are linked in pairs via As-0-As bonds to form pyroarsenate (AS207) groups. Alpha-TiAS2O7 is isostructural with a polymorph Of SiP2O7; beta-TiAS207 is a new structure.