Homochiral Emissive Λ8 - and Δ8 -[Ir8 Pd4 ]16+ Supramolecular Cages

Diego Rota Martir; Daniel Escudero; Denis Jacquemin; David B Cordes; Alexandra M Z Slawin; Herbert A Fruchtl; Stuart L Warriner; Eli Zysman-Colman

doi:10.1002/chem.201703273

Homochiral Emissive Λ₈ - and Δ₈ -[Ir₈ Pd₄ ]¹⁶⁺ Supramolecular Cages

Chemistry. 2017 Oct 12;23(57):14358-14366. doi: 10.1002/chem.201703273. Epub 2017 Sep 12.

Authors

Diego Rota Martir¹, Daniel Escudero², Denis Jacquemin^{2

3}, David B Cordes¹, Alexandra M Z Slawin¹, Herbert A Fruchtl¹, Stuart L Warriner⁴, Eli Zysman-Colman¹

Affiliations

¹ Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK.
² CEISAM UMR CNRS 6230, Université de Nantes, 2 rue de la Houssinière, BP 92208, 44322, Nantes Cedex 3, France.
³ Institut Universitaire de France, 1, rue Descartes, 75005, Paris Cedex 5, France.
⁴ School of chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK.

Abstract

Synthetic self-assembly is a powerful technique for the bottom-up construction of discrete and well-defined polyhedral nanostructures resembling the spherical shape of large biological systems. In recent years, numerous Archimedean-shaped coordination cages have been reported based on the assembly of bent monodentate organic ligands containing two or more distal pyridyl rings and square-planar Pd^II ions. The formation of photoactive Pd^II metallamacrocycles and cages, however, remain rare. Here we report the first examples of emissive and homochiral supramolecular cages of the form [Ir₈ Pd₄ ]¹⁶⁺ . These cages provide a suitably sized cavity to host large guest molecules. Importantly, encapsulation and energy transfer have been observed between the blue-emitting NBu₄ [Ir(dFppy)₂ (CN)₂ ] guest and the red-emitting Δ₈ -[Ir₈ Pd₄ ]¹⁶⁺ cage.

Keywords: cage compounds; iridium; palladium; photochemistry; self-assembly.