Abstract
Single diastereomer, diamagnetic, octahedral Fe(II) tris chelate complexes are synthesised that contain three pendant pyridine proligands pre-organised for coordination to a second metal. They bind Cu(I) and Ag(I) with coordination geometry depending on the identity of the metal and the detail of the ligand structure, but for example homohelical (ΔFe,ΔCu) configured systems with unusual trigonal planar Cu cations are formed exclusively in solution as shown by VT-NMR and supported by DFT calculations. Similar heterobimetallic tris(triazole) complexes are synthesised via clean CuAAC reactions at a tris(alkynyl) complex, although here the configurations of the two metals differ (ΔFe,ΛCu), leading to the first optically pure heterohelicates. A second series of Fe complexes perform less well in either strategy as a result of lack of preorganisation.
Highlights
2-pyridinecarboxaldehyde and one equivalent of Fe(ClO4)2· 6H2O led to the formation of a complex of the type shown in Fig. 2 fac,ΔFe,RC-[FeL13](ClO4)[2]. This complex formed as a single diastereomer (d.r. > 200 : 1) as shown by NMR spectroscopy.[8,9]
Pure heterobimetallic Fe–Cu and Fe–Ag helicates can be synthesised via the pre-formed monometallic Fe(II) complexes of L1 and L2
In both cases only a single isomer was observed by 1H NMR spectroscopy and corresponding Density functional theory (DFT) calculations predict the ΔΔ homochiral isomer will form exclusively
Summary
Pure heterobimetallic helicates from self-assembly and click strategies†. Diamagnetic, octahedral Fe(II) tris chelate complexes are synthesised that contain three pendant pyridine proligands pre-organised for coordination to a second metal. They bind Cu(I) and Ag(I) with coordination geometry depending on the identity of the metal and the detail of the ligand structure, but for example homohelical (ΔFe,ΔCu) configured systems with unusual trigonal planar Cu cations are formed exclusively in solution as shown by VT-NMR and supported by DFT calculations. Similar heterobimetallic tris(triazole) complexes are synthesised via clean CuAAC reactions at a tris(alkynyl) complex, here the configurations of the two metals differ (ΔFe,ΛCu), leading to the first optically pure heterohelicates. A second series of Fe complexes perform less well in either strategy as a result of lack of preorganisation
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