Controllable Synthesis of Centrosymmetric/Noncentrosymmetric Phases for the Family of Halogen-Based Photonic Coordination Polymers to Enhance the Phase-Matching Second-Harmonic-Generation Response.

The nonlinear-optical (NLO) materials with second-harmonic-generation (SHG) response need to crystallize in the noncentrosymmetric space group. It is very difficult to control the synthetic conditions to solely form a noncentrosymmetric phase for the materials with noncentrosymmetric and centrosymmetric conformations. Herein, we found that the temperature and halogen anion play an important role during the formation procedure of the pure noncentrosymmetric or centrosymmetric phase for the halogen-based family of coordination polymers to yield hybrid materials with a phase-matching SHG response as well as inherit the primary excellent photonic property of organic linkers. Our results provide a good choice for the design and construction of novel materials with a particular photonic property.