Homochiral Emissive Λ8‐ and Δ8‐[Ir8Pd4]16+ Supramolecular Cages
نویسندگان
چکیده
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 PdII ions. The formation of photoactive PdII 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.
منابع مشابه
Self-selecting homochiral quadruple-stranded helicates and control of supramolecular chirality.
Enantiomeric M4L4 helical cages have been prepared whose supramolecular chirality is induced by the chemical chirality of the self-sorting amino acid-derived ligands that are used. Using scrambled diastereomeric ligands or achiral glycine-derived ligands yields analogous complexes yet 'turns off' the supramolecular chirality by producing centrosymmetric cages.
متن کاملHomochiral Self‐Sorted and Emissive IrIII Metallo‐Cryptophanes
The racemic ligands (±)-tris(isonicotinoyl)-cyclotriguaiacylene (L1), or (±)-tris(4-pyridyl-methyl)-cyclotriguaiacylene (L2) assemble with racemic (Λ,Δ)-[Ir(ppy)2 (MeCN)2 ]+ , in which ppy=2-phenylpyridinato, to form [{Ir(ppy)2 }3 (L)2 ]3+ metallo-cryptophane cages. The crystal structure of [{Ir(ppy)2 }3 (L1)2 ]⋅3BF4 has MM-ΛΛΛ and PP-ΔΔΔ isomers, and homochiral self-sorting occurs in solution,...
متن کاملTripodal oxazoline-based homochiral coordination cages with internal binding sites.
Homochiral coordination cages, which have two well-defined internal binding sites for ammonium and organoammonium ions, have been constructed by Pd(II)-mediated self-assembly of preorganized tripodal oxazolines containing pyridine pendant groups.
متن کاملUnderstanding gas capacity, guest selectivity, and diffusion in porous liquids.
Porous liquids are a new class of material that could have applications in areas such as gas separation and homogeneous catalysis. Here we use a combination of measurement techniques, molecular simulations, and control experiments to advance the quantitative understanding of these liquids. In particular, we show that the cage cavities remain unoccupied in the absence of a suitable guest, and th...
متن کاملConstitutional self-sorting of homochiral supramolecular helical single crystals from achiral components.
Double-helical architectures obtained from achiral ligands and metal ions present supramolecular homochirality in the single -crystal state under constitutional self-sorting.
متن کامل