Modulation of Third-Order Nonlinear Optical Properties by Backbone Modification of Polymeric Pillared-Layer Heterometallic Clusters

Three polymeric heterothiometallic clusters with 3D pillar‐layer‐alternating honeycomblike frameworks are synthesized by a one‐pot self‐assembly reaction. Z‐scan experiments demonstrate that the nonlinear optical (NLO) behavior of these clusters can be modulated by modifying the conjugated chain of the connecting backbone ligands (see figure). Time‐dependent density functional theory calculations support and rationalize the observed NLO modulation.