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The gold(i)···lead(ii) interaction: a relativistic connection.
Raquel Echeverría1, José M López-de-Luzuriaga1, Miguel Monge1
1Departamento de Química , Universidad de La Rioja , Centro de Investigación en Síntesis Química (CISQ) , Complejo Científico-Tecnológico , 26004-Logroño , Spain .
Chemical Science
|November 17, 2017
Summary
This study reveals a strong, unsupported interaction between gold(I) and lead(II) in a novel complex. This metallophilic interaction is crucial for the complex's light emission properties in the solid state.
Area of Science:
- Inorganic Chemistry
- Solid-State Chemistry
- Computational Chemistry
Background:
- Metallophilic interactions, particularly those involving gold(I) and heavy p-block elements, are of significant interest.
- Understanding these interactions is key to designing novel materials with specific electronic and photophysical properties.
Purpose of the Study:
- To investigate the crystal structure and electronic properties of the complex [Pb{HB(pz)3}Au(C6Cl5)2] 1.
- To elucidate the nature and strength of the Au(I)···Pb(II) interaction.
- To correlate the observed metallophilic interaction with the complex's luminescence.
Main Methods:
- Single-crystal X-ray diffraction to determine the crystal structure.
- Photoluminescence spectroscopy to analyze emission properties in the solid state.
- Ab initio calculations to quantify the interaction energy and its components.
Main Results:
- The crystal structure of complex 1 exhibits an unsupported Au(I)···Pb(II) interaction.
- The complex emits light at 480 nm in the solid state.
- Calculations confirm a strong closed-shell interaction (-390 kJ mol⁻¹) with significant ionic, dispersive, and relativistic contributions (>17%).
Conclusions:
- The unsupported Au(I)···Pb(II) interaction is a key feature of complex 1.
- This metallophilic interaction is essential for the observed charge-transfer luminescence.
- Relativistic effects play a substantial role in strengthening this unique interaction.
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