Growing Crystalline Chalcogenidoarsenates in Surfactants: From Zero-Dimensional Cluster to Three-Dimensional Framework

Abstract

Although surfactants have been widely used to tailor the size, shape, and surface properties of nanocrystals and control the pore size and phases of mesoporous frameworks, the use of surfactants as reaction media to grow chalcogenide crystals is unprecedented. In addition, compared with ionic liquids, surfactants are much cheaper and can have multifunctional properties such as acidic, basic, neutral, cationic, anionic, or even block. These features suggest that surfactants could be promising reaction platforms for the development of novel chalcogenide crystals. In this work, we used chalcogenidoarsenates as a model system to demonstrate our strategy. By using three different surfactants as reaction media, we obtained a series of novel thioarsenates ranging from a zero-dimensional (0D) cluster to a three-dimensional (3D) framework, namely, [NH(4)](8)[Mn(2)As(4)S(16)] (1), [Mn(NH(3))(6)][Mn(2)As(2)S(8)(N(2)H(4))(2)] (2), [enH][Cu(3)As(2)S(5)] (3), and [NH(4)][MnAs(3)S(6)] (4). The band gaps (estimated from the steep absorption edges) were found to be 2.31 eV for 1 (0D), 2.46 eV for 2 (1D), 1.91 eV for 3 (2D), and 2.08 eV for 4 (3D). The magnetic study of 4 indicated weak antiferromagnetic behavior. Our strategy of growing crystalline materials in surfactants could offer exciting opportunities for preparing novel crystalline materials with diverse structures and interesting properties.

Solvothermal syntheses of three new one-dimensional ternary selenidostannates: [DBNH][M1/2Sn1/2Se2] (M=Mn, Zn, Hg)

“…In order to obtain chalcogenides with novel structures and unique properties, several synthetic methods have been developed, such as high-temperature solid-state reactions, room-temperature solution processes, hydrothermal/solvothermal methods, and recently emerged ionthermal/surfactantthermal methods [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]. Mild solvothermal method has been proven to be an efficient approach to prepare these materials.…”

Threading Chalcogenide Layers with Polymer Chains

“…[9] Continuing with this research, we believe that this reaction system could be a promising media to encapsulate polymer chains within inorganic matrices because surfactants have good solubility of polymers as a surfactant itself is a polymer. In this study, we firstly report the single-crystal growth of the polymer/chalcogenide complex [DBNH] (3), has been synthesized at a higher reaction temperature under the same reaction conditions.…”

Solvothermal syntheses, crystal structures, and properties of new lanthanide compounds based on tetraselenidoantimonate and tetraethylenepentamine mixed ligands

“…Chalcogenides of group 15 metals have drawn increasing interest due to their structural diversity, and potential applications in many areas such as fast-ion conductivity, semiconductivity, photo-catalyst, nonlinear optical material [1][2][3][4][5][6][7][8]. In the past decade, solvothermal synthesis in a coordinative amine media has proven to be a useful approach to the ternary chalcogenidoantimonates containing transition metal (TM) components [9][10][11][12][13], since the cobalt thioantimonate [Co(en) 3 ]CoSb 4 S 8 was prepared by the reaction of CoBr 2 and Na 3 SbS 3 in ethylenediamine (en) at 130°C [14].…”

“…complexes ions [15][16][17][18][19][20][21][22][23]. Only a few ternary chalcogenidoantimonates integrated with TM were prepared in en and dien, and the examples include Cr(en) 2 SbS 3 [24], [Mn 2 (en) 2 (Sb 2 S 5 )] [25], [Mn 2 (dien)(Sb 2 S 5 )] [26], [Mn 4 (-en) 9 (SbSe 4 ) 4 ] 4- [27], [Mn 2 (SbSe 4 ) 2 (en) 4 (H 2 O)] 2- [28], and (dienH 3 )[(dienH)MnSb 8 S 15 ] H 2 O [29]. On the other hand, the TM n?…”