Abstract
The manuscript described the synthesis and characterization of the new [Cd(BDMPT)2](ClO4)2; 1 and [Cd2(MBPT)2(H2O)2Cl](ClO4)3.4H2O; 2 s-triazine pincer-type complexes, where BDMPT and MBPT are 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine and 2-methoxy-4,6-bis(2-(pyridin-2-ylmsethylene)hydrazinyl)-1,3,5-triazine respectively. The synthesized complexes were characterized using Fourier-transform infrared spectroscopy (FTIR), 1H and 13C NMR spectroscopy, and the single-crystal X-ray diffraction technique. The homoleptic mononuclear complex (1) contains a hexa-coordinated Cd(II) center with two tridentate N-pincer ligand (BDMPT) with a highly distorted octahedral coordination environment located as an intermediate case between the octahedron and trigonal prism. The heteroleptic dinuclear complex (2) contains two hepta-coordinated Cd(II) coordination spheres where each Cd(II) is coordinated with one pentadentate pincer N-chelate (MBPT), one water, and one bridged chloride ligand connecting the two metal ions. The different intermolecular interactions in the studied complexes were quantified using Hirshfeld analysis. Their thermal stabilities and FTIR spectra were compared with the corresponding free ligands. The strength and nature of Cd–N, Cd–O, and Cd–Cl coordination interactions were discussed in light of atoms in molecules calculations (AIM). The M(II)–BDMPT and M(II)–MBPT interaction energies revealed that such sterically hindered ligands have higher affinity toward large-size metal ions (M = Cd) compared to smaller ones (M = Ni or Mn).
Highlights
The structure crystallized in the orthorhombic crystal system and Cmca space group with Z = 8
It should be noted that only half of the complex is crystallographically space group with
It should be noted that only half of the complex is crystallographically independent; the asymmetric unit of this complex comprised half of its molecular formula
Summary
The self-assembly technique is the most simple and direct way used in inorganic chemistry to construct supramolecular extended metal organic frameworks [1,2,3], in which the molecular units are held together by strong metal–ligand interactions or weaker non-covalent interactions [4,5,6,7,8,9,10].In this context, 1,3,5-triazine (s-triazine) derivatives are attractive building blocks to construct metal complexes due to their versatile coordination modes [11,12,13,14,15,16] and excellent ability to form coordination compounds with interesting extended supramolecular architectures [17,18,19].Coordination compounds of Cd(II) attracted much interest due to their fluorescence properties where Cd(II) has the ability to change the emission characteristics of ligand to which it is coordinated [20].Cd(II) complexes have interesting photochemical and photophysical properties [21,22,23].In addition, Cd(II) complexes of organic ligands rich in nitrogen are important energetic materials [24].Crystals 2019, 9, 226; doi:10.3390/cryst9050226 www.mdpi.com/journal/crystals. The self-assembly technique is the most simple and direct way used in inorganic chemistry to construct supramolecular extended metal organic frameworks [1,2,3], in which the molecular units are held together by strong metal–ligand interactions or weaker non-covalent interactions [4,5,6,7,8,9,10] In this context, 1,3,5-triazine (s-triazine) derivatives are attractive building blocks to construct metal complexes due to their versatile coordination modes [11,12,13,14,15,16] and excellent ability to form coordination compounds with interesting extended supramolecular architectures [17,18,19].
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