Crystallographic Aspects, Photophysical Properties, and Theoretical Survey of Tetrachlorometallates of Group 12 Metals [Zn(II), Cd(II), and Hg(II)] with a Triply Protonated 2,4,6-Tris(2-pyridyl)-1,3,5-triazine Ligand

Zn(II) (complex 1), Cd(II) (complex 2), and Hg(II) (complex 3) complexes have been synthesized using a triply protonated tptz (H3tptz3+) ligand and characterized mainly by single-crystal X-ray analysis. The general formula of all of the complexes is (H3tptz)3+·Cl–·[MCl4]2–·nH2O (where n = 1, 1.5, and 1.5 for complexes 1, 2, and 3, respectively). The crystallographic analysis reveals that the anion···π, anion···π+, and several hydrogen bonding interactions play a fundamental role in the stabilization of the self-assembled architectures that in turn help to enhance the dimensionality of all of the complexes. In addition, Hirshfeld surfaces and fingerprint plots have been deployed here to visualize the similarities and differences in hydrogen bonding interactions in 1–3, which are very important in forming supramolecular architectures. A density functional theory (DFT) study has been used to analyze and rationalize the supramolecular interactions by using molecular electrostatic potential (MEP) surfaces and combined QTAIM/NCI plots. Then, the device parameters for the complexes (1–3) have been thoroughly investigated by fabricating a Schottky barrier diode (SBD) on an indium tin oxide (ITO) substrate. It has been observed that the device made from complex 2 is superior to those from complexes 1 and 3, which has been explained in terms of band gaps, differences in the electronegativities of the central metal atoms, and the better supramolecular interactions involved. Finally, theoretical calculations have also been performed to analyze the experimental differences in band gaps as well as electrical conductivities observed for all of the complexes. Henceforth, the present work combined supramolecular, photophysical, and theoretical studies regarding group 12 metals in a single frame.