Dimethylaniline-Based Hybrid Compounds of Cadmium Diiodide: Synthesis, Crystal Structure, and Physical Properties

In this work, synthesis, crystal structure, and selected properties of two new organic-inorganic compounds based on cadmium iodide with 2,5- and 2,6-dimethylaniline: CdI2(2,5-DMA)(2) 1 and CdI2(2,6-DMA)(2) 2, respectively, were investigated. Both compounds were obtained using the same methodology, and their crystal structures were determined from powder (1) and single-crystal (2) X-ray diffraction experiments. The examined materials crystallize in the noncentrosymmetric space group Fdd2 and contain large polarizable iodine ions and electron-rich aromatic ligands. Second harmonic generation (SHG) tests performed with urea as a reference revealed high SHG efficiency of powdered samples 1 and 2. SHG signals measured for samples 1 and 2 are, respectively, around 10 and 8 times larger than the signal for urea. The experimental part was supplemented with theoretical calculations of the second-order electric susceptibility tensor components, chi((2))(ijk). Calculated values of the chi((2))(113) tensor component around 1.2-1.4 pm.V-1 suggest that both materials are relatively efficient second harmonic generators. Fibrous morphology of the materials was revealed by scanning electron microscopy (SEM), and the observed bending of the fibers suggested their significant flexibility. Samples 1 and 2 were also characterized by spectroscopic techniques (IR, RS, UV-Vis-DRS) and their thermal stability and decomposition rates were researched using XRPD and TG/DSC, revealing that both investigated materials are thermally stable up to around 100 degrees C.