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Updated: Jul 24, 2026

Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies
Published on: November 28, 2013
Gold(I) and silver(I) metallocryptates based on 2,9-bis(diphenylphosphino)-1,8-naphthyridine
V J Catalano1, H M Kar, B L Bennett
1Department of Chemistry, University of Nevada, Reno, Reno, Nevada 89557. vjc@unr.edu
This study synthesized novel gold and silver complexes using the rigid diphosphine ligand 2,9-bis(diphenylphosphino)-1,8-naphthyridine (dppn). These complexes, featuring encapsulated sodium or silver ions, exhibit interesting structural and emissive properties.
Area of Science:
- Coordination Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- The synthesis of novel metal complexes with unique structural and electronic properties is crucial for advancing materials science.
- Diphosphine ligands, such as 2,9-bis(diphenylphosphino)-1,8-naphthyridine (dppn), offer versatile coordination modes for metal ions.
- Exploring the self-assembly of metal-ligand systems can lead to the formation of complex supramolecular architectures.
Purpose of the Study:
- To synthesize and characterize new gold and silver complexes using the dppn ligand.
- To investigate the structural features and encapsulation of metal ions within these complexes.
- To explore the photophysical properties, specifically luminescence, of the synthesized compounds.
Main Methods:
- Reactions of (SMe2)AuCl and AgNO3 with dppn in acetonitrile.
- Isolation and purification of the resulting metal complexes.
- Characterization using 31P(1H) NMR spectroscopy, electronic absorption spectroscopy, X-ray crystallography, emission spectroscopy, and elemental analysis.
- Further characterization of gold complex 1 by cyclic voltammetry and mass spectrometry.
Main Results:
- Synthesis of a sodium-encapsulating gold complex, [Au2Na(mu-dppn)3](PF6)3 (1), and a silver complex, [Ag2(mu-dppn)3Ag](PF6)3 (3).
- X-ray crystallography revealed that complexes 1 and 3 feature a three-coordinate metal capping a metallocryptate with an encapsulated ion.
- Complex 1 exhibits Au...Na interactions of ~3.5 Å, while complex 3 shows a short Ag...Ag interaction of 3.145(2) Å.
- Complex 1 was found to be emissive, similar to its lithium, potassium, and cesium analogues.
Conclusions:
- The dppn ligand can effectively coordinate with gold and silver ions to form intricate metallocryptate structures.
- The encapsulation of alkali and coinage metal ions within these dppn-based frameworks leads to unique structural arrangements.
- The emissive properties of these complexes suggest potential applications in luminescent materials.
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