Observation of in Situ Ligand Reactions during the Assembly of Crystalline Zn−S Clusters

Six new neutral crystalline clusters Zn8S(SC6H5)14L2 [L = pyridyl (1), 3-(phenylthio)pyridyl (2), 4-(phenylthio)pyridyl (3), 3-iodopyridyl (4), 3-butylpyridyl (5), and phenanthridyl (6)] with Zn8S cores have been assembled by a hydrothermal process. Exceptionally, in situ ligand reactions have been observed in clusters 2 and 3. There are no detectable fluorescence emissions of complexes 1−5, whereas 6 shows an emission peak at 365 nm due to the existence of terminal phenanthridyl ligands.