New insight into the metal-ligand binding interaction in meso-2,3-dimercaptosuccinic acid (DMSA) protected silver nanoclusters (NCs) is presented in this work. IR, Raman and C-13 NMR spectroscopic characterizations and DFT calculations suggest that DMSA forms a bidentate binding, rather than the originally-proposed monodentate binding, via two sulfur atoms with the underlying Ag-7 NC, which is in agreement with recent ab initio calculations. (C) 2011 Elsevier B.V. All rights reserved.