Zero- and one-dimensional thioindates synthesized under solvothermal conditions yielding α-In2S3, β-In2S3 or MgIn2S4 as thermal decomposition products

Quiroga‐González, Enrique; Kienle, Lorenz; Näther, Christian; Chakravadhanula, Venkata Sai Kiran; Lühmann, Henning; Bensch, Wolfgang

doi:10.1016/j.jssc.2010.09.024

Cited by 15 publications

(6 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The adamantane-like [In 4 S 10 H 4 ] 4– cluster is constructed by four {InS 3 SH} units through sharing S corners and thus can be classified into the T2 category (Figure a). 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 .…”

Section: Resultssupporting

confidence: 73%

“…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. 77,78 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.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

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

et al. 2021

View full text Add to dashboard Cite

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.

show abstract

Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 99%

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

et al. 2021

View full text Add to dashboard Cite

show abstract

“…As far as we know, the alkaline earth metal−amine complexes were seldom documented for being used as SDAs in the formation of thioindates or thioantimonates. 59,60 In compound 3, [Mg-(dien) 2 ] 2+ complexes play the structure-directing role together with extra H 2 O molecules and balance the negative charge of the anionic layers. These complexes interconnect with the layers into a 3D supramolecule through extensive N−H···S, N− H···O, and C−H···S hydrogen bonds, Figure 6.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…As far as we know, the alkaline earth metal−amine complexes were seldom documented for being used as SDAs in the formation of thioindates or thioantimonates. 59,60 In compound Notably, the inorganic layer of our earlier reported [(Me) 2 NH 2 ] 2 [In 2 Sb 2 S 7 ] 43 as well as those in compounds 2 and 3 possesses an exactly identical composition of In:Sb:S = 2:2:7, motivating us to compared them in detail from a structural viewpoint. For clarity, here, we abbreviate these three types of layers in [(Me) 2 NH 2 ] 2 [In 2 Sb 2 S 7 ], 2, and 3 as In 2 Sb 2 S 7 -I, In 2 Sb 2 S 7 -II, and In 2 Sb 2 S 7 -III, respectively.…”

Section: ■ Results and Discussionmentioning

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

View full text Add to dashboard Cite

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.

show abstract

“…An example of organo‐In complexed with a mixed alkydithiocarbamate ligand, [Et 2 In(S 2 CNMe n Bu)], gave β ‐In 2 S 3 thin films using the standard MOCVD method , . Alkyl thiolates, thiobenzoates, thiocarbazates, thiobiurets, thiophosphinates and thiocarboxylates, are also examples of SSPs which have been exploited in the fabrication of In x S y nanoparticles and thin films displaying different phases and diverse morphological features.…”

Section: Introductionmentioning

confidence: 99%

Important Phase Control of Indium Sulfide Nanomaterials by Choice of Indium(III) Xanthate Precursor and Thermolysis Temperature

et al. 2019

View full text Add to dashboard Cite

Four In(III) xanthate complexes, [In(S2COR)3] where R = Me, Et, iPr and sBu, respectively, were synthesized, characterized and subsequently used as single source molecular precursors via a solventless thermolysis route to obtain indium sulfide materials. By choice of precursor and reaction temperature crystalline powders of tetragonal In2S3, cubic In2S3 and cubic In2.77S4 were acquired. The phase identification and purity were conducted through examination of the experimental powder X‐ray diffraction patterns relative to the simulated patterns for single X‐ray crystal diffraction.

show abstract

Zero- and one-dimensional thioindates synthesized under solvothermal conditions yielding α-In2S3, β-In2S3 or MgIn2S4 as thermal decomposition products

Cited by 15 publications

References 45 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

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

Important Phase Control of Indium Sulfide Nanomaterials by Choice of Indium(III) Xanthate Precursor and Thermolysis Temperature

Contact Info

Product

Resources

About