Related Experiment Video
Updated: Dec 16, 2025
Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
Published on: June 7, 2018
Spectroscopic and structural studies, thermal characterization, optical proprieties and theoretical investigation of
Abstract:
In this study we present the crystal structure, spectroscopic and thermal behavior, Hirshfeld surface analysis, and DFT calculations of a new organic-inorganic hybrid compound (C7H8N3)2[CoCl4]. This compound crystallizes in the centrosymmetric space group P1¯. Single-crystal X-ray diffraction analysis indicates that structure consists of a succession of mixed layers formed by organic cations and inorganic anions parallel to the (001) plane and propagate according to the c-axis. Layers further are assembled into a 3D supramolecular architecture through N-H…Cl hydrogen bonds and π…π interactions. The peak positions of the experimental PXRD pattern are in agreement with the simulated ones from the crystal structure, indicating phase purity of the title compound. The presence of the different functional groups and the nature of their vibrations were identified by ATR-FTIR and FT-Raman spectroscopies. The tetrahedral environment of Co2+ was confirmed by UV-visible spectroscopy, where the spectrum shows three weak absorption bands in the visible range due to d-d electronic transitions 4A2(F) → 4T2(F), 4A2(F) → 4T1(F) and 4A2(F) → 4T1(P) typical of Co(II) coordination compounds. The direct and indirect optical band gap values were determined by Tauc method. The optimized structure and calculated vibrational frequencies were obtained by density functional theory (DFT) using B3LYP functional. TGA and DSC coupled to mass spectrometry (MS) experiments under argon atmosphere in the temperature range (25-950 °C) were carried out in order to determine the thermal stability of the title compound.
Related Concept Videos
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
02:42Valence Bond Theory
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
02:34Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
02:27Predicting Molecular Geometry