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Hydrogen-bonded networks through second-sphere coordination.

Derek A Beauchamp1, Stephen J Loeb

  • 1Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, N9B 3P4, Canada.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|November 2, 2002
PubMed
Summary
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Researchers discovered that 4,7-phenanthroline forms hydrogen-bonded networks with metal aqua complexes, not coordination complexes. This supramolecular interaction, M-O-H...N, offers a new method for crystal engineering and creating novel metal-containing polymers.

Area of Science:

  • Supramolecular Chemistry
  • Crystal Engineering
  • Coordination Chemistry

Background:

  • 4,7-phenanthroline is a known N-donor ligand.
  • Transition metal aqua complexes are common coordination compounds.
  • Coordination complexes typically form between metal cations and N-donor ligands.

Purpose of the Study:

  • To investigate the reaction of 4,7-phenanthroline with various transition metal aqua complexes.
  • To explore the formation of supramolecular hydrogen-bonded networks as an alternative to direct coordination.
  • To demonstrate the utility of this hydrogen bonding motif in crystal engineering.

Main Methods:

  • Reaction of 4,7-phenanthroline with aqueous transition metal complexes ([Mn(H2O)6][NO3]2, [Co(H2O)6][NO3]2, [Ni(H2O)6[NO3]2, [Mn(H2O)6][ClO4]2, and [Co(H2O)6][ClO4]2).

Related Experiment Videos

  • X-ray crystallography to determine five crystal structures: [Co(H2O)4(NO3)2].(1)2, [Co(MeCN)2(H2O)4][ClO4]2.(1)2, [Ni(H2O)4(NO3)2].(1)2, [Mn(H2O)4(NO3)2].(1)2, and [Mn(H2O)6][ClO4]2.(1)(4).4H2O.
  • Thermogravimetric analysis to assess material stability.

    • Main Results:

    • Unexpected formation of supramolecular hydrogen-bonded networks instead of coordination complexes.
    • Identification of M-O-H...N interactions between coordinated water molecules and 4,7-phenanthroline.
    • Five crystal structures confirmed the generality of this hydrogen bonding scheme, involving M-O-H...N(1) and M-O-H...O(anion) interactions.
    • Thermogravimetric analysis indicated stabilities comparable to coordination polymers.

    Conclusions:

    • The reaction of 4,7-phenanthroline with transition metal aqua complexes leads to supramolecular networks via hydrogen bonding, not direct coordination.
    • This M-O-H...N hydrogen bonding motif serves as a versatile building block for crystal engineering.
    • Second-sphere hydrogen bonding shows significant potential for constructing novel polymeric metal-containing materials.