Related Experiment Video
Updated: Apr 21, 2026
06:53
Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
2.5K
Intermolecular interactions in solid-state metalloporphyrins and their impacts on crystal and molecular structures
Seth C Hunter1, Brenda A Smith, Christina M Hoffmann
1Department of Chemistry, The University of Tennessee , Knoxville, Tennessee 37996, United States.
Inorganic Chemistry
|October 24, 2014
Summary
Intermolecular interactions significantly impact metalloporphyrin crystal structures, causing disorder and phase changes. Understanding these interactions is key to analyzing metalloporphyrin complexes.
Area of Science:
- Solid-state chemistry
- Crystallography
- Materials science
Background:
- Metalloporphyrins are crucial in various chemical and biological processes.
- Understanding their solid-state structures is vital for predicting their properties and reactivity.
- Previous studies suggested structural complexities in related complexes.
Purpose of the Study:
- To investigate the role of intermolecular interactions in the crystal structure disorder of [Fe(TPP)Cl].
- To analyze phase transitions in nitrosyl complexes [M(TPP)(NO)] (M = Fe, Co).
- To elucidate structural similarities and differences among these metalloporphyrins.
Main Methods:
- Variable-temperature (VT) X-ray crystallography.
- Neutron diffraction studies.
- Hirshfeld surface analysis.
- Void-volume calculations.
Main Results:
- Intermolecular interactions are identified as a major cause of crystal structure disorder in [Fe(TPP)Cl] and [M(TPP)(NO)].
- Significant structural disorder (8-fold) in [M(TPP)(NO)] at room temperature obscures metal-nitrosyl binding.
- Phase transition in [Co(TPP)(NO)] correlates with increased void volume and phenyl ring tilting.
- Phenyl group tilting in [Fe(TPP)Cl] at low temperatures is attributed to intermolecular forces.
Conclusions:
- Intermolecular forces play a critical role in dictating the solid-state behavior of metalloporphyrins.
- Hirshfeld surface analysis and void-volume calculations effectively characterize structural variations.
- These findings provide insights into the structure-property relationships of metalloporphyrin complexes.
Related Concept Videos
02:54Molecular and Ionic Solids
16.3K
Crystalline solids are divided into four types: molecular, ionic, metallic, and covalent network based on the type of constituent units and their interparticle interactions.
Molecular Solids
Molecular crystalline solids, such as ice, sucrose (table sugar), and iodine, are solids that are composed of neutral molecules as their constituent units. These molecules are held together by weak intermolecular forces such as London dispersion forces, dipole-dipole interactions, or hydrogen bonds, which...
Molecular Solids
Molecular crystalline solids, such as ice, sucrose (table sugar), and iodine, are solids that are composed of neutral molecules as their constituent units. These molecules are held together by weak intermolecular forces such as London dispersion forces, dipole-dipole interactions, or hydrogen bonds, which...
16.3K
02:58Crystal Field Theory - Octahedral Complexes
28.3K
Crystal Field Theory
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...
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...
28.3K
02:37Metallic Solids
16.3K
Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and...
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and...
16.3K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
47.4K
Tetrahedral 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...
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...
47.4K
01:09Complexation Equilibria: Factors Influencing Stability of Complexes
985
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
985
03:00Intermolecular vs Intramolecular Forces
90.5K
Intermolecular forces (IMF) are electrostatic attractions arising from charge-charge interactions between molecules. The strength of the intermolecular force is influenced by the distance of separation between molecules. The forces significantly affect the interactions in solids and liquids, where the molecules are close together. In gases, IMFs become important only under high-pressure conditions (due to the proximity of gas molecules). Intermolecular forces dictate the physical properties of...
90.5K