Novel Copper(I)‐Thioantimonates(III): Solvothermal Synthesis,Crystal Structures,Thermal Stability and Magnetic Properties of (C2N2H10)0.5Cu2SbS3, (C3N2H12)0.5Cu2SbS3, and (C4N2H14)0.5Cu2SbS3 |
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Authors: | Volker Spetzler,Herme Rijnberk,Christian N ther,Wolfgang Bensch |
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Affiliation: | Volker Spetzler,Herme Rijnberk,Christian Näther,Wolfgang Bensch |
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Abstract: | The novel copper(I)‐thioantimonates(III) (enH22+)0.5Cu2SbS3 ( I ) (en = ethylendiamine), (1, 3‐DAPH22+)0.5Cu2SbS3 ( II ) (1, 3‐DAP = 1, 3 diaminopropane) and (1, 4‐DABH22+)0.5Cu2SbS3 ( III ) (1, 4‐DAB = 1, 4‐diaminobutane) were synthesized under solvothermal conditions reacting Sb2S3, CuCl2·2H2O, S with the amines. The compounds crystallize in the monoclinic space group P21/n. The primary building units are a SbS3 trigonal pyramid and two distorted CuS3 units. In the structures the SbS3 pyramid is connected to six CuS3 moieties and every S atom has bonds to one Sb atom and to two Cu atoms. Further interconnection leads to the formation of ten‐membered (10 MR) Cu3Sb2S5 and six‐membered (6 MR) Cu2SbS3 rings. Every 10 MR is condensed to four 10 MR and four 6 MR to form a single layer within the (010) plane. Two such single layers are connected to a double layer thus forming the final [Cu2SbS3]— layered anion. The [CuSbS3]— protonated amines are located between the layers and the interlayer spacing depends on the size and orientation of these amines. Between the Sb atom and one Cu atom a remarkable short distance of about 2.7Å is observed. At elevated temperatures the compounds decompose into CuSbS2 and Cu3SbS4 suggesting a complex redox reaction. Diamagnetic susceptibilities indicate the copper(I) in the metal sulfide frameworks. All three compounds are semiconductors with intermediate band gaps of about 2 eV. |
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Keywords: | Copper Thioantimonates Solvothermal synthesis Crystal structure Spectroscopy Thermal investigations Magnetic properties |
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