Chiral silver and gold rings: synthesis and structural, spectroscopic, and photophysical properties of Ag and Au metallamacrocycles of bridging NHC ligands

Carcedo, Cristina, Knight, James Christopher, Pope, Simon J. A. ORCID: https://orcid.org/0000-0001-9110-9711, Fallis, Ian Andrew ORCID: https://orcid.org/0000-0001-7361-0182 and Dervisi, Athanasia ORCID: https://orcid.org/0000-0002-0590-5496 2011. Chiral silver and gold rings: synthesis and structural, spectroscopic, and photophysical properties of Ag and Au metallamacrocycles of bridging NHC ligands. Organometallics 30 (9) , pp. 2553-2562. 10.1021/om200125w

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Abstract

The synthesis and silver(I) and gold(I) coordination chemistry of a new chiral, bidentate N-heterocyclic carbene (NHC) dehydrohexitol derivative (3) are reported. The imidazolium salt [H23][PF6]2 reacts with Ag2O and Au(tht)Cl (tht = tetrahydrothiophene) precursors to form the isostructural 18-membered metallamacrocyclic dimers [Ag2(μ-3)2][PF6]2 and [Au2(μ-3)2][PF6]2 and the monocarbene complex [(AuCl)2(μ-3)]. Single-crystal X-ray structures have been determined for the bis-imidazolium precursor [H23][PF6]2 and corresponding Ag(I) and Au(I) complexes of ligand 3. Comparison between the X-ray-derived structures and solution-phase NMR data for [Ag2(μ-3)2][PF6]2 and [Au2(μ-3)2]- [PF6]2 demonstrate that the complexes adopt a conformation in solution different from that found in the solid state, implying a conformational flexibility of the metallamacrocycle in solution. Both [(AuCl)2(μ-3)] and [Au2(μ-3)2][PF6]2 are emissive in the solid state at ca. 380 nm (λex = 295 nm). Time-resolved luminescence measurements indicate different excited-state lifetimes for the two species, with [(AuCl)2(μ-3)] measured at 35 ns and [Au2(μ-3)2][PF6]2 at 379 ns. The chiroptical properties of the silver and goldNHCcomplexes have been studied by circular dichroism (CD).

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	American Chemical Society
ISSN:	0276-7333
Last Modified:	18 Oct 2022 13:12
URI:	https://orca.cardiff.ac.uk/id/eprint/12910

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