Mu‐35: A Fluorogallophosphate Obtained by In Situ Generation of the Template

Abstract

A two‐dimensional microporous fluorogallophosphate, named Mu‐35, closely related to ULM‐8, was hydrothermally synthesized by in situ generation of the structure‐directing agent. The precursor of the structure‐directing agent is ethylformamide, which is generated in situ by decomposition, and goes on to form ethylamine molecules that act as templates in the medium used for the synthesis. The fluorogallophosphate Mu‐35 (Mu is Mulhouse), Ga3(PO4)2(HPO4)F3(C2H8N)2(C2H7N)0.5 (Z = 8), crystallizes in the orthorhombic space group Pbcn with the following unit cell parameters: a = 22.117(1), b = 17.3740(8), c = 10.1550(4) Å. The structure of fluorogallophosphate Mu‐35 was determined from single‐crystal XRD data. It exhibits anionic layers composed of an unusual arrangement of three‐, five‐, and eight‐membered rings (MR) [Ga2PO2F, Ga3P2O4F, and Ga3P3O8, respectively], and intercalated by protonated and nonprotonated ethylamine molecules. Mu‐35 was also characterized by powder XRD, SEM, elemental and thermal analyses, and solid‐state NMR spectroscopy (1H, 13C, 19F, and 31P MAS and 1H‐31P HETCOR experiments). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

A Multinuclear Solid-State NMR Study of Templated and Calcined Chabazite-Type GaPO-34

“…The synthesis of gallium phosphate analogues was a natural extension to this work, given that the Ga–O tetrahedral bond length is only slightly longer than that of tetrahedral Al–O . A diverse range of GaPOs has now been synthesized, with the large number prepared by the “fluoride route” of particular note. , For example, the striking tetrahedral framework material known as cloverite, which contains rings made up of 20 tetrahedral centers, was first prepared as a gallium phosphate by this method, later leading to the discovery of doped variants and a pure AlPO form . It is typical, especially when the fluoride route is employed, for five- and six-coordinate gallium environments to occur alongside four-coordinate gallium in many phosphates …”

Synthesis of microporous gallophosphates obtained by in situ decomposition of hexamethylphosphoramide

“…Thus numerous aluminophosphates and gallophosphates were obtained by this synthesis route. It was the case of the aluminophosphates Mu-4 [9], Mu-7 [10] and the gallophosphates Mu-30 [11], Mu-34 [12], Mu-35 [13], Mu-37 [14], Mu-38 [15] and Ea-TRENGaPO [16].…”

Fluorinated mixed valence Fe(ii)–Fe(iii) phosphites with channels templated by linear tetramine chains. Structural and magnetic implications of partial replacement of Fe(ii) by Co(ii)

“…16 In spite of the scientific community has made progress in the rational organic SDAs-mediated synthesis of zeolitic inorganic open framework materials, 4 the complex chemical reaction mechanisms in which the inorganic buildings nucleate around the organic cationic species are still poorly understood. Actually, there are many examples in which the SDAs represent the products of the initial organic precursors transformed during the hydrothermal synthesis by means of hydrolysis of linear polyamines, 17 decomposition of amides 18 or N-alkylation reactions. 19 Therefore, because of the large number of parameters involved in the reaction processes still make the rational approach to the synthesis of these materials a challenging task, the "trial-and-error" strategy becomes necessary to explore new architectures when new organic templates are being used.…”

“…Actually, there are many examples in which the SDAs represent the products of the initial organic precursors transformed during the hydrothermal synthesis by means of hydrolysis of linear polyamines, 17 decomposition of amides 18 or N-alkylation reactions. 19 Therefore, because the large number of parameters involved in the reaction processes still make the rational approach to the synthesis of these materials a challenging task, the "trial-and-error" strategy becomes necessary to explore new architectures when new organic templates are being used.…”