Surfactant-Thermal Syntheses, Structures, and Magnetic Properties of Mn–Ge–Sulfides/Selenides

Abstract

Although either surfactants or amines have been investigated to direct the crystal growth of metal chalcogenides, the synergic effect of organic amines and surfactants to control the crystal growth has not been explored. In this report, several organic bases (hydrazine monohydrate, ethylenediamine (en), 1,2-propanediamine (1,2-dap), and 1,3-propanediamine (1,3-dap)) have been employed as structure-directing agents (SDAs) to prepare four novel chalcogenides (Mn3Ge2S7(NH3)4 (1), [Mn(en)2(H2O)][Mn(en)2MnGe3Se9] (2), (1,2-dapH)2{[Mn(1,2-dap)2]Ge2Se7} (3), and (1,3-dapH)(puH)MnGeSe4(4) (pu = propyleneurea) under surfactant media (PEG-400). These as-prepared new crystalline materials provide diverse metal coordination geometries, including MnS3N tetrahedra, MnGe2Se7 trimer, and MnGe3Se10 T2 cluster. Compounds 1-3 have been fully characterized by single-crystal X-ray diffraction (XRD), powder XRD, UV-vis spectra, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Moreover, magnetic measurements for compound 1 showed an obvious antiferromagnetic transition at ~9 K. Our research not only enriches the structural chemistry of the transitional-metal/14/16 chalcogenides but also allows us to better understand the synergic effect of organic amines and surfactants on the crystallization of metal chalcogenides.

Surfactants as Promising Media for the Preparation of Crystalline Inorganic Materials

“…During our continuing research on the preparation of crystalline metal chalcogenides, a series of manganese chalcogenidogermanates, Mn 3 Ge 2 S 7 (NH 3 ) 4 (2D), [Mn(en) 2 (H 2 O)] [Mn(en) 2 MnGe 3 Se 9 ] (1D), (1,2‐dapH) 2 {[Mn(1,2‐dap) 2 ]Ge 2 Se 7 } (1D), and (1,3‐dapH)(puH)MnGeSe 4 (1D; pu=propyleneurea), were synthesized in the surfactant PEG‐400 in the presence of different organic amines (hydrazine monohydrate, ethylenediamine, 1,2‐propanediamine (1,2‐dap), 1,3‐propanediamine (1,3‐dap)) 57. The surfactant PEG‐400 was crucial to the formation of these compounds, since no crystal could be obtained without the addition of PEG‐400.…”

Unprecedented 3D and 2D Frameworks of Manganese Thioarsenates Based on Heterometallic Cubic Cluster [Mn6(µ6‐S)(AsS3)4] and Covalent Linker N2H4

“…The seventh crystallographically independent Mn 2+ cations in 1 and 2 are coordinated by two tridentate dien ligands and three bidentate 1,2‐dap ligands to form [Mn(dien) 2 ] 2+ and [Mn(1,2‐dap) 3 ] 2+ complex cations (Figures S7 and S8), respectively. The Mn–N bond lengths of 2.162(19)–2.308(17) Å in 1 and 2.243(12)–2.359(11) Å in 2 (Table ) are in agreement with those observed in [Mn(dien) 2 ] 2+ and [Mn(1,2‐dap) 3 ] 2+ complexes,[5f], respectively. The Mn–N bond lengths have no distinct differences to the bond lengths between Mn II and hydrazine molecules (Table ).…”

A Discrete Ligand-Free T3 Supertetrahedral Cluster of Gallium Sulfide

“…While Kanatzidis and co-workers have exploited surfactants in solutions for the preparation of mesostructured phases from T2 [Ge 4 Q 10 ] 4− clusters (where Q = S, Se) [ 24 ], for crystalline chalcogenides the “surfactant-thermal” approach has primarily been applied to thioarsenates [ 25 , 26 ] and thioantimonates [ 27 , 28 ]. Reports of crystalline supertetrahedra-based chalcogenides prepared by the “surfactant-thermal” method appear to be limited to [Mn(en) 2 (H 2 O)][Mn(en) 2 MnGe 3 Se 9 ] (where en = ethylenediamine), which contains chains of T2 clusters [ 29 ]. To the best of our knowledge, this methodology has not previously been applied to gallium sulfides.…”