Synthesis and structure of [(Ph₃P)₂Cu(μ-SeCH₂Ph)₂In(SeCH₂Ph)₂] as a single-source precursor for the preparation of CuInSe₂ nano-materials

Abstract

The complex [(Ph3P)2Cu(μ-SeCH2Ph)2In(SeCH2Ph)2] has been synthesized and structurally characterized, which on solvolysis yielded single phasic CuInSe2 nanoparticles. The particles were characterized by pXRD, SEM, HRTEM, EDX and DRS analysis.

The use of mixed-metal single source precursors for the synthesis of complex metal oxides

“…141 Mixed-metal selenides are also obtainable from the related precursors [(Ph3P)2MIn(SeC{O}R)4] (M = Cu, Ag, R = Ph, tolyl) 142 or [(Ph3P)2CuIn(SeCH2CPh)4]. 143 Complex metal fluorides are also accessible, for example, coordination polymers NaM(hfac)4 (M=Y, Eu, Gd or Er, hfac= hexafluoroacetylacetonate) can be decomposed to give NaMF4 materials (with both kinetic and thermodynamic polymorphs accessible) (Fig. 17d), 144,145…”

Systematic Access of Ternary Organotetrel‐Copper Chalcogenide Clusters by [PhTE3]3− Anions (T=Si, Sn; E=S, Se)

“…Although the lowest absorption energies of 5 and 6 are perfectly reproduced by the calculations, we find a systematical overestimation of the values for the organotin-based clusters 7, 8, and 9. The deviation towards slightly larger energies amounts to 0.4 (9), 0.5 (8) or 1.0 eV (7), which for the two first (and in part for the latter) case is based on the relatively complicated mixture of transitions involved in this first excitation in case of the organotin clusters. Inspection of the calculated HOMO-LUMO gaps confirm that the results of the TD-DFT treatment are reasonable.…”

“…[ 1 , 2 ] Discrete complexes and clusters of such compositions have received a lot of attention in recent times owing to their potential as precursors to said materials, as showcased for CuInE 2 (E=S, Se), a promising semiconductor material for energy conversion in solar cells. [ 3 , 4 , 5 , 6 , 7 ] For this reason, many activities in this direction so far have addressed group 13 compounds, be it as supertetrahedral anions[ 8 , 9 , 10 , 11 , 12 ] or as neutral cages. [ 13 , 14 , 15 , 16 , 17 ] Krautscheid and co‐authors have published a series of investigations on compounds exhibiting organic substituents at the group 13 metal, such as [R 3 PCu) 4 (MeM) 4 E 6 ] (R=organic substituent; M=Ga, In).…”

“…As with the group 13 clusters, tin containing T5-type supertetrahedral anions, e. g., [Cu 2 Ga 16 Sn 2 S 35 ], [28] as well as cages with ligand-free tin atoms, like [Cu 6 Sn 6 S 20 ] 10À , [29][30][31] have been reported. Notably, there is also one study about analogous Pb complexes [{(PPh 3 ) 3 } Cu 5 (μ-SPh) 7 Pb] and [Pb(μ-SPh) 4 {Cu(PPh 3 ) 2 } 2 ]. [32] Regarding organo-functionalized clusters, a synthesis from mononuclear compounds is possible, [33] but most of the reported clusters were synthesized by transformations of binary cage compounds of the general formulas [(RSn) 4 E 6 ] or [(RSn) 3 E 4 Cl] (R = organic substituent, E = S, Se).…”

“…Ternary chalcogenide compounds of copper and a p‐block metal, in particular CuSn(S/Se)‐based materials, are currently actively investigated because of their opto‐electronic as well as their thermoelectric properties [1,2] . Discrete complexes and clusters of such compositions have received a lot of attention in recent times owing to their potential as precursors to said materials, as showcased for CuInE 2 (E=S, Se), a promising semiconductor material for energy conversion in solar cells [3–7] . For this reason, many activities in this direction so far have addressed group 13 compounds, be it as supertetrahedral anions [8–12] or as neutral cages [13–17] .…”