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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Triiodide-Based Chair-Like Copper Complex Assembled by Halogen Bonding.

Mikhail A Kinzhalov1,2, Ekaterina I Kinzhalova1, Valentina A Karnoukhova3

  • 1Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation.

Inorganic Chemistry
|December 18, 2023
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Summary

New copper-iodide polyiodide crystals were synthesized by cocrystallizing copper complexes with iodine. These novel materials exhibit unique supramolecular structures driven by halogen bonding interactions.

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Area of Science:

  • Inorganic Chemistry
  • Supramolecular Chemistry
  • Crystal Engineering

Background:

  • Copper-iodide complexes are known for their diverse structural motifs.
  • Cocrystallization is a powerful technique for creating novel materials with tailored properties.
  • Polyiodide anions can form complex structures with metal centers.

Purpose of the Study:

  • To synthesize and characterize novel copper-iodide polyiodide cocrystals.
  • To investigate the formation of new supramolecular architectures through cocrystallization with iodine.
  • To explore the role of halogen bonding in stabilizing these structures.

Main Methods:

  • Cocrystallization of dimeric and polymeric copper-iodide complexes with molecular iodine.
  • Single-crystal X-ray diffraction analysis to determine crystal structures.
  • Theoretical calculations to analyze halogen bonding interactions.

Main Results:

  • Formation of a series of (RNC)2CuI-based crystal polyiodides.
  • Discovery of a novel supramolecular motif in polyiodide 5·2I2, featuring a Cu2(μ1,3-I3)2 core in a chair conformation.
  • Identification of moderately strong halogen bonding (I···I contacts) as the driving force for the observed supramolecular architecture.

Conclusions:

  • Cocrystallization of copper-iodide complexes with iodine provides access to novel polyiodide materials.
  • The polyiodide 5·2I2 showcases a unique inorganic halogen-bonded core with a chair conformation.
  • Halogen bonding plays a crucial role in dictating the supramolecular assembly and stability of these copper-iodide polyiodides.