New Members of the Family of In–Sb–S Compounds: Different Roles of Organic Amines

Abstract

Reported here are the syntheses, structures, and characterizations of four novel In−Sb−S compounds containing organic amines, namely, [PAH] 3 [In 3 Sb 2 S 9 ] (PA = npropylamine) (1), [Fe(en) 3 ][In 2 Sb 2 S 7 ] (en = ethylenediamine) (2), [Mg(dien) 2 ][In 2 Sb 2 S 7 ]·0.5H 2 O (dien = diethylenetriamine) (3), and In 2 (N,N-dmen) 2 Sb 2 S 6 (N,N-dmen = N,N-dimethylethylenediamine) (4). Compound 1 features a [In 3 Sb 2 S 9 ] n 3n− layer assembled by the alternating linkage of the {In 2 Sb 2 S 8 } n ribbons and the {In 4 Sb 2 S 12 } n double-ribbons. Both compounds 2 and 3 possess layered anionic parts with the same stoichiometry of [In 2 Sb 2 S 7 ] n 2n− but distinct linkage modes between the subunits of {In 2 S 7 } groups and Sb 3+ ions. Notably, the {In 2 Sb 2 S 9 } heterometallic cluster observed in 3 is initially regarded as the secondary building unit (SBU) for the construction of the [In 2 Sb 2 S 7 ] n 2n− layer. Compound 4 features a novel discrete inorganic−organic hybrid molecule of In 2 (N,N-dmen) 2 Sb 2 S 6 . Through the structural analyses on 1−4, the organic amines applied played three different roles on the formation of the final crystalline products. For 1, the protonated n-propylamines arrange in the space around the anionic network and balance the negative charge. For 2 and 3, the chelating polyamines coordinate to central metal ions to form metal complexes, which then act as space-filling and charge-balancing agents. For 4, two N,N-dimethylethylenediamines chelate to two In 3+ ions of the inorganic segment through coordination bonds, leading to the formation of a rare inorganic−organic hybrid cluster. At last, we gave a systematic discussion about the characteristics and roles of organic amines in all related In−Sb−S compounds. In one word, the work presented here enriches the structural chemistry of the main-group heterometallic chalcogenidometalates, providing more chances for researchers to work out the rules in their composition− or structure−function relationship.

Mixed Solvothermal Synthesis of Tn Cluster-Based Indium and Gallium Sulfides Using Versatile Ammonia or Amine Structure-Directing Agents

“…Ammonia/amine represents one class of effective SDAs for the synthesis of metal chalcogenides. , First, these molecules can easily undergo protonation to form ammonium/alkylammonium cations that compensate for the negative charge of inorganic moieties. − Second, they can also be directly bonded to the corner of T n cluster when a lone pair of electrons of the N atom, acting as a Lewis base, is donated into an empty sp 3 hybrid orbital on the metal center. − Third, the variety in size and conformation endows these SDAs with better adaptability to the cavities and channels in the solid. − Fourth, the surfactant-like amines that consist of hydrophilic −NH x groups and hydrophobic carbon skeletons would take appropriate orientations in crystal lattice and form crucial N–H···Q (Q = S, Se, and Te) hydrogen-bonding interactions with the inorganic constituent. − With the intense effort expended to develop new T n cluster-based chalcogenides, the challenge with structure-directing methodology is to explore the pronounced effects of ammonia/amine on the solid architecture in a more systematic way.…”

“…Mixed solvothermal synthesis emerged as an effective method for the incorporation of ammonia/amine into the solid product. The solvent composition, which determines the solubility, reactivity, and diffusion of the reagents, has a significant effect on the crystal nucleation and growth. − Recently, we have prepared metal chalcogenides by taking advantage of the amine–ethanol mixtures ,,, and the deep eutectic solvents (DESs). − In the present work, the mixed solvothermal approaches are applied for the synthesis of four novel T n cluster-based indium and gallium sulfides, namely, [NH­(CH 3 ) 3 ] 4 ­In 4 S 10 H 4 ( 1 ), (NH 3 ) 4 Ga 4 S 6 ( 2 ), [NH 3 CH 2 CH 3 ] 5 ­(NH 2 CH 2 CH 3 ) 2 Ga 11 S 19 ( 3 ), and [NH 3 CH 2 ­CH 2 OH] 6 Ga 10 S 18 ·2NH 2 ­CH 2 CH 2 OH ( 4 ). With a special focus on the structure-directing mechanism, we investigate the effects of ammonia/amine in full respect of bonding, space filling, local coordination, and weak interactions.…”

“…The solvent composition, which determines the solubility, reactivity, and diffusion of the reagents, has a significant effect on the crystal nucleation and growth. 48−51 Recently, we have prepared metal chalcogenides by taking advantage of the amine−ethanol mixtures 18,21,22,36 and the deep eutectic solvents (DESs). 52−56 In the present work, the mixed solvothermal approaches are applied for the synthesis of four novel (4).…”

The solvothermal synthesis and characterization of quaternary arsenic chalcogenides CsTMAsQ3 (TM = Hg, Cd; Q = S, Se) using Cs+ as a structure directing agent: from 1D anionic chains to 2D anionic layers

“…Generally, chalcogenides can be prepared using several traditional methods, including a high temperature solid-state approach, molten ux methods, electrochemical methods and hydrothermal thermal methods. [9][10][11] Since the study by Bedard et al 12 was published in 1989, the solvothermal synthesis of main-group chalcogenidometalates using amines has attracted extensive attention, as it is a signicant method for the synthesis of chalcogenides. 1, 9 During the past few decades, owing to the diversity of the bonding modes of the chalcogen atoms, the stereochemical effect of the lone electron pairs and the various coordination orientations of As/Sb(III) by sulfur/ selenium atoms, large structural and compositional diversities have been observed for multinary chalcogenides, and therefore a large number of metal chalcogenides compounds have been prepared.…”

“…[9][10][11] Since the study by Bedard et al 12 was published in 1989, the solvothermal synthesis of main-group chalcogenidometalates using amines has attracted extensive attention, as it is a signicant method for the synthesis of chalcogenides. 1, 9 During the past few decades, owing to the diversity of the bonding modes of the chalcogen atoms, the stereochemical effect of the lone electron pairs and the various coordination orientations of As/Sb(III) by sulfur/ selenium atoms, large structural and compositional diversities have been observed for multinary chalcogenides, and therefore a large number of metal chalcogenides compounds have been prepared. Recently, it has been reported that in the combination of the structural units of As x Q y (Q ¼ S, Se) the As III ions tend to adopt the diverse AsQ n (Q ¼ S, Se) (n ¼ 3-6) ligands that can share corners and/or edges with transition metal ions (TM ¼ Ag + , Cu 2+ , Mn 2+ ), 11,[13][14][15][16][17][18][19][20][21][22][23][24] and could form interesting structural various multinary chalcogenides, 8 such as 1D chains, 2D layers, 3D framework.…”