Ionothermal synthesis, crystal structure and solid-state NMR spectroscopy of a new organically templated gallium oxalatophosphate: (H2TMPD)0.5[Ga3(C2O4)0.5(PO4)3] (TMPD = N,N,N′,N′-tetramethyl-1,3-propanediamine)

Abstract

A new organically templated gallium oxalatophosphate, (C7H20N2)0.5[Ga3(C2O4)0.5(PO4)3], has been synthesized by using a low-melting-point eutectic mixture of choline chloride and oxalic acid as a solvent and characterized by single-crystal X-ray diffraction, thermogravimetric analysis and solid-state NMR spectroscopy. It is the first example of ionothermal synthesis of organically templated metal oxalatophosphate. The structure contains double 6-ring units of the composition Ga6(PO4)6 which are connected by oxalate ligands and P-O-Ga bonds to form a 3-D framework. The charge-compensating organic ammonium cations which are disordered over two positions are located at the intersections of two types of 8-ring channels. 1H MAS and 13C CPMAS NMR studies confirm the presence of N,N,N',N'-tetramethyl-1,3-propanediammonium cation. The 71Ga and 31P MAS NMR spectra are also consistent with the crystal structure analysis results.

Layered Zinc Phosphates with Photoluminescence and Photochromism: Chemistry in Deep Eutectic Solvents

“…Following the yellow-green phosphor NTHU-7, [4] we have synthesized the first metal-activator-free orange phosphor NTHU-9, which has a unique layered structure of zinc chlorophosphate with occluded organic templates ( Figure 1). [4,9] Intriguingly, by careful scrutiny in both reaction products and filtrates, we identified unexpected fragments which led us to discover two concurrent pathways of chemical reactions involving choline ions under ionothermal conditions (Scheme 1): 1) demethylation of choline ions to give methylium (CH 3 + ) ions and 2-(dimethylamino)ethanol (DMAE); 2) hydrolysis of choline ion to ethylene glycol (EG) and trimethylamine, which further reacts with CH 3 + to give the tetramethylammonium (TMA) ions. [4,9] Intriguingly, by careful scrutiny in both reaction products and filtrates, we identified unexpected fragments which led us to discover two concurrent pathways of chemical reactions involving choline ions under ionothermal conditions (Scheme 1): 1) demethylation of choline ions to give methylium (CH 3 + ) ions and 2-(dimethylamino)ethanol (DMAE); 2) hydrolysis of choline ion to ethylene glycol (EG) and trimethylamine, which further reacts with CH 3 + to give the tetramethylammonium (TMA) ions.…”

Ionothermal Synthesis of Zirconium Phosphates and Their Catalytic Behavior in the Selective Oxidation of Cyclohexane

“…The nature of the interaction between the solvent and reacting species is undoubtedly critical, not only for control over the final crystal structure of the products, but also their crystal size and morphology, [6] both of which are important for synthetic chemists and materials scientists. Choosing the proper solvent is vital to the success or failure of the attempted syntheses.Ionothermal synthesis, a new method for the preparation of aluminophosphate molecular-sieve analogues [7][8][9][10][11][12][13][14] and other materials, [15][16][17][18] was developed in 2004 and has interesting features and potential advantages over the traditional method of molecular-sieve synthesis. For example, the cation of the ionic liquid can act both as the solvent and the structure-directing agent, and synthesis can take place at ambient pressure, eliminating safety concerns associated with high solvent pressures.…”

Ionothermal synthesis and crystal structure of a 2D metal organic framework: [emim]2[Cd2(btec)Br2] (emim=1-ethyl-3-methylimidazolium, btec=1,2,4,5-benzenetetracarboxylate)

“…2D-[Cu(1,3-bis(4-pyridyl)propane)]BF 4 [25] and 3D-[Cu 3 (tpt) 4 ](BF 4 ) 3 Á(tpt) 2/3 Á5H 2 O (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine] [26] represent the first two MOFs obtained ionothermally. Recent examples include some other 2D [15,19,25] and 3D MOFs [15,16,18,[21][22][23][24]26]. Nevertheless, there are still relatively rare examples of MOFs prepared in ionic liquids to date [27,28].…”

“…Compared with coventional volatile organic solvents, ILs are designable, environmentally benign and recyclable for sustainable chemistry [10,11]. Recently, ionothermal synthesis have shown high promise in the preparation of novel inorganic or organic-inorganic hybrid materials such as inorganic nanoparticles [11], zeolites and zeotype materials [12][13][14] and metal organic frameworks (MOFs) [15][16][17][18][19][20][21][22][23][24][25][26]. Under ionothermal conditions, ILs not only may serve as solvent [15,17], but also function as templates, charge compensating groups and/or coordination ligands with their cations [15,16,23,24] or anions [25,26] or both [18][19][20] present in the resulting structures.…”