(DEA-H)+7In11S21H2: a new layered open framework indium sulfide based on the interconnection of [In10S20]10− supertetrahedra

Pitzschke, Dragan; Näther, Christian; Bensch, Wolfgang

doi:10.1016/s1293-2558(02)01374-2

Cited by 30 publications

(18 citation statements)

References 16 publications

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“…The In–S b (b, bridging) bond lengths of the cluster lie in the range 2.435(2)–2.454(2) Å which is comparable to the common values in the literature. , In comparison, this cluster exhibits relatively long In–S t (t, terminal) bond lengths ranging from 2.460(2) to 2.471(2) Å. This is in contrast to many Ge–S, Ga–S, or In–S materials that contain the T2-[M 4 S 10 ] n ‑ (M = Ge, Ga, In) thioanion whose terminal bond lengths are obviously shorter than the bridging ones because of the stronger bonding. ,, Bond valence sum (BVS) calculations on the terminal S1, S2, S3, and S4 atoms indicate the one negative charge for each (Table S1), suggesting that these terminal S atoms are actually −SH groups . This identification was confirmed by the FTIR spectrum, where the weak peak at 2513 cm –1 can be assigned to the S–H vibration (Figure S7).…”

Section: Resultssupporting

confidence: 73%

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

et al. 2021

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Metal chalcogenide supertetrahedral Tn clusters are of current interest for their unique compositions and structures, which rely highly on the structure-directing agents. Herein, we report four novel Tn 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). All four compounds were solvothermally synthesized in mixed amine−ethanol solutions or deep eutectic solvent (DES), where ammonia/amine molecules play significant structure-directing roles in the speciation and crystal growth. (1) Being protonated, the trimethylamine and ethanolamine molecules surround the T2-[In 4 S 10 H 4 ] 4− clusters (for 1) and [Ga 10 S 18 ] n 6n− open framework (for 4), respectively, compensating for the negative charge of the inorganic moieties. (2) With the lone pair of electrons, the ammonia molecules in 2 coordinate directly to corner Ga 3+ ions of the {Ga 4 S 6 } cage to give a neutral T2-(NH 3 ) 4 Ga 4 S 6 cluster. (3) For compound 3, part of the ethylamine molecules act as terminating ligands for the T1 and T3 units in the [Ga 11 S 19 (NH 2 CH 2 CH 3 ) 2 ] n 5n− layer, while the rest act as interlamellar countercations upon protonation. Theoretical studies reveal the contributions of N, C, and H to the density of states (DOS) for 2 and 3 because of their hybrid structures that combine the ammonia/amine ligands with sulfide moieties together.

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Section: Resultssupporting

confidence: 73%

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

et al. 2021

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“…The majority of the thioindates were obtained under solvothermal conditions in the presence of organic amines as structure‐directing agents. The structures of these compounds are commonly based on InS 4 tetrahedra or their supertetrahedral clusters, and the size of the clusters appears to correlate with the size of the organic amines 13–17…”

Section: Introductionmentioning

confidence: 99%

Solvothermal Synthesis and Characterization of One‐dimensional Indium Polyselenides with Transition Metal Complexes

Yao

et al. 2012

Zeitschrift anorg allge chemie

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Two different systems were used for syntheses of metal selenides, [Mn(en) 3 ][In 2 Se 5 ] (1) and [MnSe(en) 0.5 ] (2) by the reactions of In 2 Se 3 , MnCl 2 , and selenium powder at 170°C for 6 days. Compound 1 contains a one-dimensional [In 2 Se 5 ] 2chain propagating along the crystallographic c axis separated by [Mn(en) 3 ] 2+ complex cations. The anionic chain is constructed by vertex-linked InSe 4 tetrahedra linked

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“…Actually, the protonated amines have surfactant-like behavior, where the hydrophilic group (containing N atom) has a higher tendency to facing the anionic network while the hydrophobic group (carbon skeleton) likes pointing toward the void around the framework. 67,68 So the position of the N atom in the organic amine may somehow affect the fitness between the SDA and inorganic host.…”

Section: In−sb−s Architectures Containing Organic Aminesmentioning

confidence: 99%

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

Wang

Zhang

et al. 2014

Crystal Growth & Design

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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.

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(DEA-H)+7In11S21H2: a new layered open framework indium sulfide based on the interconnection of [In10S20]10− supertetrahedra

Cited by 30 publications

References 16 publications

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

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

Solvothermal Synthesis and Characterization of One‐dimensional Indium Polyselenides with Transition Metal Complexes

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

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