Organic-Inorganic Hybrid Noncentrosymmetric (Morpholinium)₂Cd₂Cl₆ Single Crystals: Synthesis, Nonlinear Optical...

To design nonlinear optical (NLO) materials, we focused on combinations of d¹⁰ metal cation (Cd²⁺)-based chloride and morpholine molecules to form organic-inorganic hybrids. The O of morpholine containing lone-pair electrons can be integrated with Cd²⁺ by a ligand-to-metal charge transfer (LMCT) strategy to build acentric structures benefiting from the second-order Jahn-Teller effect. Introduction of the high-electronegativity chlorine can make polyhedrons of acentric crystals more distorted and conducive to a strong second harmonic generation (SHG) response. Therefore, (Morpholinium)₂Cd₂Cl₆ crystals were constructed and synthesized by a solvent evaporation method. (Morpholinium)₂Cd₂Cl₆ belongs to the orthorhombic P2₁2₁2₁ space group and shows a one-dimensional (1D) structure with distorted [CdCl₆] and [CdCl₄O₂] octahedrons. The short cutoff edge of (Morpholinium)₂Cd₂Cl₆ was determined to be about 230 nm. The SHG response of (Morpholinium)₂Cd₂Cl₆ exhibited an intensity of approximately 0.73 × KDP as estimated by the powder second harmonic generation technique. Furthermore, related theoretical calculations were performed to study the relationship of the band structure, refractive anisotropy, electronic state, and nonlinear optical response. Besides, (Morpholinium)₂Cd₂Cl₆ showed relatively good thermal stability. This work can serve as a guide for the design and synthesis of new large NLO hybrid crystals with d¹⁰ transition metals.