Synthese und thermische Eigenschaften von molekularen Clusterverbindungen zusammengesetzt aus Elementen der Gruppen 11‐13‐16

Abstract

CuX (X = Cl, CH3COO) bzw. AgOC(O)C6H5 und GaCl3 reagieren in THF mit S(SiMe3)2 bzw. Se(SiMe3)2 in Anwesenheit von PPh3 zu [Cu6Ga8Cl4S13(PPh3)6] (1), [Cu6Ga8Cl4Se13(PPh3)6] (2), [Ag6Ga8Cl4S13(PPh3)6] (4) und [Ag6Ga8Cl4Se13(PPh3)6] (5). Verwendet man anstelle von PPh3 das Phosphan PnPr2Ph, so läßt sich nach Überschichten mit n‐Hexan die Verbindung [Cu6Ga8Cl4Se13(PnPr2Ph)12] (3a, 3b) kristallisieren. Durch Umsetzung von CuCl, GaCl3 und PnPr3 mit Se(SiMe3)2 in THF erhält man den ionischen Cluster (HPnPr3)2[Cu2Ga4Cl4Se6(PnPr3)4] (6). Die Strukturen der Verbindungen 1—6 konnten durch Einkristall‐Röntgenstrukturanalyse aufgeklärt werden. TGA‐MS‐Messungen und Pulverdiffraktogramme der Rückstände zeigen die potentielle Verwendbarkeit der Cluster als Prekursormaterialien zur Darstellung der entsprechenden ternären Festkörperverbindungen.

Synthesis and Structure of [nPr3N(CH2)6NnPr3][CuFe3Br3(SePh)6], [Cu5Fe(SePh)7(PPh3)4] and [Cu4Fe3(SePh)10(PPh3)4]

“…In this context, Kanatzidis et al have studied the suitability of mixed copper/indium chalcogenolates as precursor materials for the photovoltaic materials CuInE 2 (E = S, Se). [1,11] Corrigan et al have observed room-temperature fluorescence for the ternary 12-12Ј-16 cluster (12 = Zn; 12Ј = Cd; 16 = Se) [(N,NЈ-tmeda) 5 Zn 5 Cd 11 Se 13 (SePh) 6 (thf) 2 ], [9] while binary cadmium or zinc selenide clusters show weak luminescence only at temperatures below 50 K. [12,13] Strong infrared fluorescence behavior has been observed to occur in the heterometallic chalcogenido cluster molecules [(py) 8 Ln 4 M 2 Se 6 (SePh) 4 ] (Ln = Er; M = Cd, Hg). [10] [a] Institut für Nanotechnologie, Forschungszentrum Karlsruhe The ternary phase CuFeS 2 has been known to be a semiconductor material for a long time and was one of the first compounds to be used for the construction of radio frequency detectors, [14] while information about CuFeSe 2 is limited and only a few papers have been devoted to this compound during the last five years.…”

“…Examples of different compounds include (PPh 4 )[Cu 6 In 3 (SEt) 16 ], [1] 6 ] (M I = Cu, Ag; M III = Ga, In; E = S, Se), [2] [Cu 11 In 15 Se 16 -(SePh) 24 (PPh 3 ) 4 ], [3] [Ag 26 In 18 S 36 Cl 6 (dppm) 10 (thf) 4 ][InCl 4 -(thf)] 2 , [4] [Hg 15 Cu 20 S 25 (PnPr 3 ) 18 ], [5,6] [Cu 4 Nb 2 Se 6 (PMe 3 ) 8 ], [7] [Ta 4 Cu 12 Cl 8 S 12 (PMe 3 ) 12 ], [8] [(N,NЈ-tmeda) 5 Zn 5 Cd 11 Se 13 -(SePh) 6 (thf) 2 ], [9] and [(py) 8 Ln 4 M 2 Se 6 (SePh) 4 ] (Ln = Er, Yb, Lu; M = Cd, Hg). [10] Interest in these compounds lies in the characterization of their structures and an investigation of their properties.…”

Synthesis and Structure of Two Ionic Copper Indium Selenolate Cluster Complexes [As(C6H5)4]2[Cu6In4(SeC6H5)16Cl4] and [As(C6H5)4][Cu7In4(SeC6H5)20]

“…Examples for different classes of compounds include [Cu 6 In 3 (SEt) 16 ](PPh 4 ), [1] [M I 6 M III 8 Cl 4 E 13 (PPh 3 ) 6 ] (M I = Cu, Ag; M III = Ga, In; E = S, Se), [2] [Cu 11 In 15 Se 16 (SePh) 24 (PPh 3 ) 4 ], [3] [Ag 26 In 18 S 36 -Cl 6 (dppm) 10 (THF) 4 ][InCl 4 (THF)] 2 , [4] [Hg 15 Cu 20 S 25 (PnPr 3 ) 18 ], [5,6] [Cu 4 Nb 2 Se 6 (PMe 3 ) 8 ], [7] [Ta 4 Cu 12 Cl 8 S 12 (PMe 3 ) 12 ] [8] and [(N,N,NЈ,NЈ-tmeda) 5 Zn 5 Cd 11 Se 13 (SePh) 6 (THF) 2 ]. [9] Interest in these compounds arises for several reasons: (a) investigation of the structural build-up of a certain composition of elements with respect to existing and nonexisting bulk phases, (b) development of precursor compounds for the production of thin films of ternary materials and (c) investigation of the properties of nano-sized species.…”

Synthesis and Structure of [Ag26In18S36Cl6(dppm)10(thf)4][InCl4(thf)]2—A Combined Approach of Theory and Experiment

“…Similar to the synthetic approach for binary clusters outlined above, the reaction of mixtures of the metal halides with E(SiMe 3 ) 2 6 ], (M = Cu, Ag; M' = Ga, In; E = S, Se). [11,13] Interestingly, the stoichiometric composition and structure of the cluster molecules differ from the corresponding bulk material. We report herein the synthesis, structural characterization, and theoretical investigation of [Ag 26 In 18 S 36 Cl 6 (dppm) 10 The molecular structure of 1 has been determined by single-crystal X-ray structural analysis.…”

“…[7] Ternary compounds, however, offer a broader spectrum of tunable properties and are viable candidates for technical use, for example, CuInSe 2 is one of the most promising materials for thin-film technology in solar cells, [8] and conversion efficiencies of up to 18.8 % have been achieved with Cu(In,Ga)Se 2 under laboratory conditions; [9] AgInS 2 , AgIn 5 S 8, and AgGaS 2 are of interest as materials for non-linear optical devices. [10] This prompted us to investigate the synthesis of ternary cluster compounds composed of elements of Group 11,13,and 16. Similar to the synthetic approach for binary clusters outlined above, the reaction of mixtures of the metal halides with E(SiMe 3 ) 2 6 ], (M = Cu, Ag; M' = Ga, In; E = S, Se).…”