Coordination Chemistry of a Molecular Pentafoil Knot

The binding of Zn­(II) cations to a pentafoil (5₁) knotted ligand allows the synthesis of otherwise inaccessible metalated molecular pentafoil knots via transmetalation, affording the corresponding “first-sphere” coordination Co­(II), Ni­(II), and Cu­(II) pentanuclear knots in good yields (≥85%). Each of the knot complexes was characterized by mass spectrometry, the diamagnetic (zinc) knot complex was characterized by ¹H and ¹³C NMR spectroscopy, and the zinc, cobalt, and nickel pentafoil knots afforded single crystals whose structures were determined by X-ray crystallography. Lehn-type circular helicates generally only form with tris-bipy ligand strands and Fe­(II) (and, in some cases, Ni­(II) and Zn­(II)) salts, so such architectures become accessible for other metal cations only through the use of knotted ligands. The different metalated knots all exhibit “second-sphere” coordination of a single chloride ion within the central cavity of the knot through CH···Cl^– hydrogen bonding and electrostatic interactions. The chloride binding affinities were determined in MeCN by isothermal titration calorimetry, and the strength of binding was shown to vary over 3 orders of magnitude for the different metal-ion–knotted-ligand second-sphere coordination complexes.