Mass spectroscopic analysis revealed that Pd clusters passivated by thiolates and the stoichiometric thiolate complexes, Pdn=(SR)2n (n = 5; 6), are formed in the reactions between palladium chloride and n-alkanethiols (RSH: R = n-C18H37, n-C12H25) in toluene. The Pd clusters thus formed are formulated as Pdn(SR)m with m ∼ 0.6n. The cluster sizes, distributed in the range of 5 ≤ n ≤ 60, are consistent with their core diameters of ∼ 1 nm observed by TEM. A gap of ∼ 2 eV was observed in the optical transition of the Pdn(SR)m clusters showing the emergence of non-metallic properties as a result of size reduction.
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