Site-specific sulfur-for-metal replacement in a silver nanocluster.

A new Ag 36 nanocluster with a closed electronic structure and eight valence electrons is reported, which has a similar structure to that of an open-shell Ag 34 nanocluster with three valence electrons, except that in the shell two (Ag-PPh 3 ) + cations replace two S 2- anions specifically. The fine structural modulation leads to various levels of activity for singlet oxygen photogeneration due to the distinct optical gaps of the nanoclusters.