Metal Ions Play Different Roles in the Third‐Order Nonlinear Optical Properties of d¹⁰ Metal–Organic Clusters

Abstract

The heavy-atom effect cannot explain the difference in the third-order nonlinear optical properties of the clusters [Ag10(dcapp)4](OH)2⋅12 H2O (1, see structure), [Zn4O(dcapp)3]⋅6 H2O (2), and [Hg2(dcapp)2] (3) (H2dcapp=2,6-dicarboxamido-2-pyridylpyridine). Quantum chemical calculations show that the NLO properties of 1 are controlled both by the metal and the ligand, while those of 2 and 3 are controlled by the ligand only.