Isolation of β-Ag3AsSe3, (Me3NH)[Ag3As2Se5], K5Ag2As3Se9, and KAg3As2S5: Novel Solid State Silver Thio- and Selenoarsenates from Solvento-thermal Synthesis
✍ Scribed by Mercouri G. Kanatzidis; Jun-Hong Chou
- Publisher
- Elsevier Science
- Year
- 1996
- Tongue
- English
- Weight
- 774 KB
- Volume
- 127
- Category
- Article
- ISSN
- 0022-4596
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✦ Synopsis
have been prepared. The majority of them involve ternary Three new solid state silver selenoarsenates and one thioarse-systems associated with alkali metals and organic counternate prepared from hydro-and methanothermal synthesis ions. For example, Scha ¨fer et al. prepared a large number are described. -Ag 3 AsSe 3 (I) and (Me 3 NH)[Ag 3 As 2 Se 5 ] (II) were of ternary alkali metal antimony sulfides using the hydrosynthesized hydrothermally at 110؇C from a mixture of thermal technique, including Cs 2 Sb 8 S 13 (1) and A 2 Sb 4 S 7 (2) AgBF 4 /3K 3 AsSe 3 and AgBF 4 /3K 3 AsSe 3 /6Me 3 NHCl, while (A ϭ K, Rb, Cs). Sheldrick et al. investigated the M/Pn/ K 5 [Ag 2 As 3 Se 9 ] (III) and K[Ag 3 As 2 S 5 ] (IV) were synthesized Q system (M ϭ alkali metal, Pn ϭ As, Sb, Q ϭ S, Se) methanothermally at 110؇C from a mixture of AgBF 4 /3K 3 AsS 3 using superheated water and methanol and showed that a and AgBF 4 /3K 3 AsSe 3 , respectively. -Ag 3 AsSe 3 (I) crystallizes host of ternary phases can be prepared by reacting alkali in the orthorhombic space group Pnma (No. 62) with a ؍ metal carbonate with a binary Pn 2 Q 3 phases (3). Recently, 8.111(1) A ˚, b ؍ 11.344(2) A ˚, c ؍ 20.728(3) A ˚, Z ؍ 8, V ؍ the same methodology has been extended to tetraalkyl 1907(1) A ˚3. This compound is a new allotrope of ␣-Ag 3 AsSe 3 ammonium ions which tend to produce more open frameand has a complex three-dimensional structure composed of distorted trigonal planar and tetrahedral Ag ؉ ions and [AsSe 3 ] 3؊ works (4). Compounds involving the [Pn x Q y ] nϪ thioanions units. (Me 3 NH)[Ag 3 As 2 Se 5 ] (II) crystallizes in the triclinic space in combination with transition or main group metals are group P ؊ 1 (No. 2) with a ؍ 10.119(2) A ˚, b ؍ 18.010(4) A ˚, more rare. Kolis et al. reported several new thioarsenate c ؍ 14.932(3) A ˚, ␣ ؍ 110.20 (1)؇,  ؍ 103.98(2)؇, ␥ ؍ 99 99(1)؇, and antimonate phases from superheated ethylenedi-Z ؍ 2, V ؍ 729.3(8) A ˚3. The [Ag 3 As 2 Se 5 ] n؊ n anion in (II) has a amine, including some with metal ions which bind the thicomplex two-dimensional layered structure with tetrahedral oanions [AsS 3 ] 3Ϫ and [SbS 3 ] 3Ϫ (5). We approach the chem-Ag ؉ ions and [As 2 Se 5 ] 4؊ units. K 5 [Ag 2 As 3 Se 9 ] (III) crystallizes istry of these polyanions from a polychalcogenide viewin the orthorhombic space group Pnma (No. 62) with a ؍ point. We have shown that the hydrothermal method can 12.599(2) A ˚, b ؍ 12.607(4) A ˚, c ؍ 14.067(3) A ˚, Z ؍ 8, V ؍ be a useful synthetic route to new polychalcogenide com-2234(1) A ˚3. The [Ag 2 As 3 Se 9 ] 5n؊ n anion in (III) has a two-dimenpounds (6). Polychalcogenide ligands of various lengths can sional layered structure with tetrahedral Ag ؉ ions and two act as building blocks by connecting metal ions together to different kinds of selenoarsenate units, [AsSe 4 ] 3؊ and [As 2 Se 5 ] 4؊ . K[Ag 3 As 2 S 5 ] (IV) also crystallizes in the orthorhombic space form compounds with structures ranging from molecular to group Pnma (No. 62) with a ؍ 19.210(2) A ˚, b ؍ 16.867(2) A ˚, polymeric one-dimensional, two-dimensional, and even c ؍ 6.3491(7) A ˚, Z ؍ 8, V ؍ 2057.2(7) A ˚3. The [Ag 3 As 2 S 5 ] n؊ n three-dimensional. Since each member of a Q 2Ϫ x chain conanion in (IV) possesses a complicated two-dimensional structains at least two lone pairs of electrons, one or all atoms ture with tetrahedral Ag ؉ ions and two kinds of thioarsenate of the polychalcogenide ligand can bind to metal ions (7). ligands, [AsS 3 ] 3؊ and [As 3 S 7 ] 5؊ . The thermal stability and optical Because the As Ϫ ion is isoelectronic to S (or Se), conceptuabsorption properties of these compounds are reported. © 1996 ally, the [As x S y ] nϪ anions can be related to the well-known Academic Press polychalcogenide ligands; see Scheme 1. An excellent example for demonstration of this relationship is found in (Ph 4 P)[SAsS 7 ] (8). The eight-member crown shaped ring is
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