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Related Concept Videos

Metallic Solids02:37

Metallic Solids

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.
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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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Noncovalent attractions are associations within and between molecules that influence the shape and structural stability of complexes. These interactions differ from covalent bonding in that they do not involve sharing of electrons.
Four types of noncovalent interactions are hydrogen bonds, van der Waals forces, ionic bonds, and hydrophobic interactions.
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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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...
Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

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...

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Abiotic metallofoldamers as electrochemically responsive molecules.

Fan Zhang1, Shi Bai, Glenn P A Yap

  • 1Brown Laboratories, Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.

Journal of the American Chemical Society
|July 28, 2005
PubMed
Summary
This summary is machine-generated.

Nonbiological molecules based on salophen and salen ligands fold into helical structures when coordinated with Ni(II) or Cu(II) metals. These metallofoldamers can reorganize, showing potential for responsive materials.

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Area of Science:

  • Supramolecular Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Salen and salophen ligands are known for their coordination properties.
  • Nonbiological molecules capable of folding into defined structures are of interest for materials science.

Purpose of the Study:

  • To design, synthesize, and study novel nonbiological molecules based on salophen and salen ligands.
  • To investigate the helical folding behavior of these molecules upon metal coordination.
  • To explore the potential of these metallofoldamers as responsive materials.

Main Methods:

  • Synthesis of salophen and salen-based ligands and their metal complexes.
  • X-ray diffraction for solid-state structure determination.
  • Nuclear Magnetic Resonance (NMR) spectroscopy to study solution structures.
  • Circular Dichroism (CD) spectroscopy and optical rotation for chirality studies.
  • Electrochemical experiments to probe structural changes upon reduction.
  • Semiempirical (AM1) calculations for theoretical support.

Main Results:

  • Nonbiological molecules based on salophen and salen ligands fold into single-stranded helices in the presence of Ni(II) or Cu(II).
  • Helical structures are confirmed in both solid-state (X-ray diffraction) and solution (NMR studies).
  • Metal coordination is essential for helix formation; free ligands do not adopt helical structures.
  • Racemic metallofoldamers undergo spontaneous resolution during crystallization and readily racemize in solution, indicating easy reorganization.
  • An analogue from enantiomerically pure diamine shows strong CD signals and large specific rotation.
  • Electrochemical reduction of a Cu(II)-foldamer induces structural reorganization, supported by computational analysis.

Conclusions:

  • Salen and salophen-based metallofoldamers form stable helical structures in solution and solid-state.
  • The observed racemization and structural reorganization upon reduction highlight their potential as responsive materials.
  • These findings open avenues for designing dynamic and adaptable molecular systems.