Related Experiment Video
Updated: Nov 22, 2025
10:52
Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
3.1K
Dibenzoarsacrowns: an experimental and computational study on the coordination behaviors
Akifumi Sumida1, Ryosuke Kobayashi, Takashi Yumura
1Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Goshokaido-cho, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan. himoto@kit.ac.jp kenaka@kit.ac.jp.
Chemical Communications (Cambridge, England)
|January 8, 2021
Summary
Novel dibenzoarsacrowns selectively bind alkali metal cations and coordinate gold(I) chloride. The gold complexation enhances sodium ion capture, demonstrating a positive allosteric effect studied computationally.
Area of Science:
- Supramolecular Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- Crown ethers are known for cation binding.
- Heteroatom-fused macrocycles offer unique coordination properties.
- Gold(I) complexes are relevant in catalysis and medicine.
Purpose of the Study:
- Synthesize and characterize novel dibenzoarsacrowns.
- Investigate the cation binding and metal coordination capabilities of dibenzoarsacrowns.
- Explore the allosteric effects in metal-ligand interactions.
Main Methods:
- Synthesis of dibenzoarsacrowns.
- Size-selective alkali metal cation binding studies.
- Chemoselective coordination of gold(I) chloride (AuCl).
- Computational studies of allosteric effects.
Main Results:
- Dibenzoarsacrowns were successfully synthesized as a new class of macrocycles.
- These compounds exhibit size-selective binding of alkali metal cations.
- Arsenic atoms show chemoselective coordination to AuCl via soft Lewis acid-base interactions.
- The AuCl complex of 21-dibenzoarsacrown-7 demonstrated enhanced Na+ encapsulation compared to the bare macrocycle.
Conclusions:
- Dibenzoarsacrowns represent a novel scaffold for host-guest chemistry.
- The observed positive allosteric effect highlights the potential for cooperative binding in these systems.
- These findings open avenues for designing advanced molecular recognition and sensing materials.
Related Concept Videos
02:42Valence Bond Theory
10.2K
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...
10.2K
02:45Valence Bond Theory
45.0K
Overview of Valence Bond Theory
45.0K
02:34Structural Isomerism
20.7K
Isomerism in Complexes
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...
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...
20.7K
02:57Coordination Number and Geometry
17.7K
For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
17.7K
02:54Coordination Compounds and Nomenclature
24.7K
In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
24.7K
02:58Crystal Field Theory - Octahedral Complexes
29.1K
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...
29.1K