Hydrogen-Bond-Driven Synergistically Enhanced Hyperpolarizability: Chiral Coordination Polymers with Nonpolar...

Four chiral coordination polymers (CPs), M[(S,S)-C₁₄ H₁₄ N₂ O₆ ] and M[(R,R)-C₁₄ H₁₄ N₂ O₆ ] (M=Zn or Cd), have been exclusively synthesized in high yields with the aid of newly designed chiral ligand under hydrothermal condition. The CPs crystallizing in the orthorhombic nonpolar space group, C222₁ , reveal three-dimensional framework structures composed of MO₄ tetrahedra and the corresponding homochiral linkers. Powder second-harmonic generation (SHG) measurements indicate that the nonpolar CPs reveal very strong SHG efficiency of ca. 5-9 times that of KH₂ PO₄ and exhibit type-I phase-matching behavior. Density functional theory calculations suggest that the unusually large SHG efficiency found from the nonpolar CPs should be attributable to the synergistic effect of polarizable metal cations and enhanced hyperpolarizability in the donor-acceptor system originating from the hydrogen bonding in the coordinated linkers.