thiolates [6] having lamellar architectures (Scheme 1A,B) are generating greater curiosity recently. [3a,6,7] The structures of many of these metal thiolates have been characterized in detail and it has been established that they consist of a network of metal ions covalently linked to sulfur atoms of the alkyl thiolate anion. [8] Recently, we found that some of these metal thiolates can be delaminated into individual molecular sheets simply by adding a nonpolar organic solvent to them. [9] Quite interestingly while few of these metal thiolates get delaminated into individual sheets (for example, Pd-alkyl thiolate, Ni-alkyl thiolate, Pb-alkyl thiolate) [6] when a nonpolar solvent is added, [9a] many others are quite insoluble (Ag-alkyl thiolate, Cu-alkyl thiolate, Au-alkyl thiolate) in these solvents under normal circumstances. [10] In this premise, it would be pertinent to ask i) would it be possible to prepare metal thiolates consisting of two metal ions? ii) What would be the bulk structure of such bimetallic thiolates? and iii) What about their solubility/ dispersibility? Here, the second question assumes greater significance because one can envisage three different structural scenarios. The first one is the formation of a segregated/mixed stack where both metal thiolates exist as separate noninteracting individual lamellar sheets and the final material is nothing but a physical mixture of the individual thiolates (Scheme 1C). The second possibility is an alternating stacks where one individual metal thiolate sheet is above the second one forming an A-B-A-B type structure (Scheme 1D). The third and final possibility is a structure where both metal ions are intricately mixed and are present in each sheet of the lamellar structure (Scheme 1E). Regarding the solubility it would be interesting to see what would happen when a bimetallic thiolate is made of two metal ions of which one of the individual metal thiolate is known to be soluble type while the other is insoluble in a given solvent.Addressing this we report here the preparation of two bimetallic thiolates, namely, copper-indium thiolate and silver-indium thiolate. The reason to choose this combination of metal ions is as follows. It has been clearly shown that of these three metal ions, thiolates of copper and silver are insoluble [10a] in most of the solvents tested. In contrast, indium thiolate is readily Thiolates of single metal ions are known to exist as lamellar structures in the neat state and some of these metal thiolates can be delaminated into individual molecular sheets simply by adding a nonpolar organic solvent. It is established here that even bimetallic thiolates such as copper-indium thiolate and silver-indium thiolate exist as lamellar sheets. Each of these sheets consists of both metal ions arranged in a random fashion. It is also demonstrated that these bimetallic thiolates can be employed as single source precursors to prepare phase pure bimetallic chalcogenide nanocrystals (NCs) through mechanochemical routes by grinding them with...
