Three-dimensional gallium sulphide open frameworks

The first polymeric thiogallate with lanthanide-containing counter cation, [Dy2(en)6(μ2-OH)2]Ga4S8

“…The band gap from the well-defined abrupt absorption edge can be estimated as 4.21 eV, which can be assigned to the electronic excitation located at the Ga 4 S 4À 8 anion. Compared with bulk Ga 2 S 3 (3.3 eV) [16], there is a blue shift of the absorption edge, similar blue shift has been found in other chalcogenidogallates [C 4 NH 12 ] 6 [Ga 10 S 18 ] (4.0 eV) and [C 4 NH 12 ][Ga 20 S 35.5 (S 3 ) 0.5 O] (4.1 eV) [5].…”

“…These compounds display interesting physicochemical properties, such as adsorption, fast ion conductivity, and tunable electronic and optical properties [1]. A variety of structures, which are based on the GaQ 4 (Q = S, Se) tetrahedra or supertetrahedral clusters as building units, have been found, as exemplified by 1D ½GaS À 2 n chains constructed by GaQ 4 6 Ga 10 S 18 (DEA = diethylamine) [5], (DEA-H) 16 4 ]SbSe 4 Á 0.5en [9]. As an extension of our study of the synthesis of lanthanide chalcogenometalates, herein we report a lanthanide thiogallate [Dy 2 (en) 6 (l 2 -OH) 2 ]Ga 4 S 8 and this compound is the only example of chalcogenidogallate combined with lanthanide(III) complex cation.…”

Supercubooctahedron (Cs6Cl)2Cs5[Ga15Ge9Se48] Exhibiting Both Cation and Anion Exchange

“…[8] Some examples are T5-MnCd 6 In 28 S 52 (SH) 4 , [5] P2-Li 4 In 22 S 44 , [9] and C3,4-Cd 54 Se 32 (SPh) 48 (H 2 O) 4 . [10] The majority of these compounds contain heavy metals of the fifth period,s uch as In, Sn, or Cd, and those containing light period 4m etals are rare;t he several reported examples include Mn 6 (H 2 O) 3 (m 6 -Se)(GeSe 4 ) 4 , [11] Ge 4 S 10 (TEA-CuGS-SB1), [12] (C 4 NH 12 )Ga 10 S 18 , [13] and [(Zn 4 Ga 16 Se 33 ) 4 (Ga 2.4 Ge 1.6 Se 8 )]-(template) x , [14] of which the isolated 53-atom [Zn 4 Ga 16 Se 33 ]c luster is the largest till now. [14] Usually,t he organic countercations (e.g.,a mine species) are an essential component, simply because the majority of these compounds are crystallized under the influence of an organic template.…”

Three‐Dimensional Covalent Co‐Assembly between Inorganic Supertetrahedral Clusters and Imidazolates

“…[4] Composite materials in which chalcogenide clusters and organic functional molecules are covalently assembled into ordered 3D arrays belong to such new families of materials.The assembly of chalcogenide clusters into extended frameworks generally occurs by sharing of anionic sulfur (or selenium) sites at four corners of each cluster, leading to extended frameworks with all linkages made through inorganic components. [9] For example, 3D inorganic frameworks made from T3 (e.g., [In 10 S 20 ] 10À ), T4 (e.g., [In 16 Cd 4 S 35 ] 14À ), and T5 (e.g., [Cu 5 In 30 S 56 ] 17À ) clusters are all known. [10] This type of intercluster linkage mode (i.e., M-X-M, X = S, Se) is common, in part because of the compatibility between inter-and intracluster M À X bonds.…”

“…The SCIFs are also the first 3D covalent inorganic-organic superlattices with chalcogenide tetrahedral clusters as one of the building blocks. While 3D frameworks comprising only supertetrahedral clusters are well known, [5,9,11] all previous efforts to cross-link tetrahedral chalcogenide clusters of any composition (e.g., organic-capped Cd-S-SPh system or inorganic Ga-S system) with organic ligands have only resulted in formation of low-dimensional structures (up to 2D). [13] Formation of SCIFs depends on achieving a suitable balance among a number of factors.…”