were harvested from a dry acetonitrile solution of Cd[S 2 CN(iPr)-CH 2 CH 2 OH] 2 after one or two days and proved to be a coordination polymer in which all dithiocarbamate ligands are μ 2 ,κ 2 -tridentate, bridging two cadmium atoms and simultaneously chelating one of these. If the same solution was allowed to stand for at least several days, 2 is replaced by blocks comprising a supramolecular isomer of 2, dimeric 1, with formula {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 •2H 2 O•2MeCN, and two ligands coordinating μ 2 ,κ 2 as in 2 and the other two purely κ 2 -chelating. The time dependency correlates with the pivotal role of water in driving the conversion of "chain" 2 to "ball" 1; crystals of 2 could not be isolated from "wet" acetonitrile. When each of 1 and 2 are dissolved in solution, they exhibit comparable spectroscopic attributes ( 1 H, 13 C, and 113 Cd NMR and UV/vis), indicating the solution structures are the same. Both 1 and 2 are luminescent in the solid state with 1 being significantly brighter than 2. Greenockite CdS nanoparticles are generated by the thermal decomposition of both 1 and 2.
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