Metallophilic interaction

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In chemistry, a metallophilic interaction is a type of non-covalent attraction between heavy metal atoms. The atoms are often within Van der Waals distance of each other and are about as strong as hydrogen bonds.[1] The effect can be intramolecular or intermolecular. Intermolecular metallophilic interactions can lead to formation of supramolecular assemblies whose properties vary with the choice of element and oxidation states of the metal atoms and the attachment of various ligands to them.[2]

Nature of the interaction[edit]

This type of interaction is enhanced by relativistic effects. A major contributor is electron correlation of the closed-shell components,[2] which is unusual because closed-shell atoms generally have negligible interaction with one another at the distances observed for the metal atoms. As a trend, the effect becomes larger moving down a periodic table group, for example, from copper to silver to gold, in keeping with increased relativistic effects.[2] Observations and theory find that, on average, 28% of the binding energy in gold–gold interactions can be attributed to relativistic expansion of the gold d orbitals.[3]

An important and exploitable property of aurophilic interactions relevant to their supramolecular chemistry is that while both inter- and intramolecular interactions are possible, intermolecular aurophilic linkages are comparatively weak and easily broken by solvation; most complexes that exhibit intramolecular aurophilic interactions retain such moieties in solution.[4] One way of probing the strength of particular intermolecular metallophilic interactions is to use a competing solvent and examine how it interferes with supromolecular properties. For example, adding various solvents to gold(I) nanoparticles whose luminescence is attributed to Au–Au interactions will have decreasing luminescence as the solvent disrupts the metallophilic interactions.[4]

Applications[edit]

Gold(I) complexes can polymerize by intermolecular metallophilic interactions to form nanoparticles.[4]

The polymerization of metal atoms can lead to the formation of long chains or nucleated clusters. Gold nanoparticles formed from chains of gold(I) complexes often give rise to intense luminescence in the visible region of the spectrum.[4]

Chains of Pd(II)–Pd(I) and Pt(II)–Pd(I) complexes have been explored as potential molecular wires.[5]


References[edit]

  1. ^ Hunks, William J.; Jennings, Michael C.; Puddephatt, Richard J. (2002). "Supramolecular Gold(I) Thiobarbiturate Chemistry: Combining Aurophilicity and Hydrogen Bonding to Make Polymers, Sheets, and Networks". Inorg. Chem. 41 (17): 4590–4598. doi:10.1021/ic020178h.
  2. ^ a b c Assadollahzadeh, Behnam; Schwerdtfeger, Peter (2008). "A comparison of metallophilic interactions in group 11[X–M–PH3]n (n = 2–3) complex halides (M = Cu, Ag, Au; X = Cl, Br, I) from density functional theory". Chemical Physics Letters. 462 (4–6): 222–228. Bibcode:2008CPL...462..222A. doi:10.1016/j.cplett.2008.07.096.
  3. ^ Runeberg, Nino; Schütz, Martin; Werner, Hans-Joachim (1999). "The aurophilic attraction as interpreted by local correlation methods". J. Chem. Phys. 110 (15): 7210–7215. Bibcode:1999JChPh.110.7210R. doi:10.1063/1.478665.
  4. ^ a b c d Schmidbaur, Hubert (2000). "The Aurophilicity Phenomenon: A Decade of Experimental Findings, Theoretical Concepts and Emerging Application". Gold Bulletin. 33 (1): 3–10. doi:10.1007/BF03215477.
  5. ^ Yin, Xi; Warren, Steven A.; Pan, Yung-Tin; Tsao, Kai-Chieh; Gray, Danielle L.; Bertke, Jeffery; Yang, Hong (15 December 2014). "A Motif for Infinite Metal Atom Wires". Angewandte Chemie International Edition. 53 (51): 14087–14091. doi:10.1002/anie.201408461. PMID 25319757.