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Preparation and oscillation of absorption bands of ZnS clusters

Electric-field-induced transient pore formation (electroporation) in DOPC vesicles is used for the preparation of molecular ZnS clusters. The absence of caps permits (a) continued growth of the ZnS clusters formed, (b) the assessment of their true absorption spectra unaltered by stabilizing ligands, and (c) the previously inaccessible live observation of the growth of the clusters in the molecular-size regime. The ensuing self-aggregation of ZnS is slowed down to month timescales by its adsorption at the exterior surface of the vesicles. The growth of the clusters in the molecular size regime is found to exhibit novel, time-dependent, oscillating red- and blue-shifts of the characteristic UV absorption band in a certain special condition. On the basis of similarities between the oscillating trend of the experimentally observed transition energy and that of the calculated HOMO–LUMO gap of (ZnS)n clusters with n = 1–9, the wavelengths of the sequential spectral peaks can be assigned to the ZnS monomer (ZnS, 217 nm), dimer ((ZnS)2, 253 nm), tetramer ((ZnS)4, 225 nm), heptamer ((ZnS)7, ∼250 nm) and nonamer ((ZnS)9, 228 nm).