A new twist in anion binding: metallo-helicate hosts for anionic guests

The condensation of 5-chlorocarbonyl-2,2'-bipyridine with a variety of rigid aromatic diamines, L, gave a series of new bisamido-2,2'-bipyridine based ligands (L = 4,4'-methylenediamine, L1; L = 1,1-bis(4-aminophenyl)cyclohexane, L2; L = 1,1-bis(4-amino-3,5-dimethylphenyl)cyclohexane, L3) capable of forming dinuclear triple helicate complexes on coordination to Fe(II). The reaction of various Fe(II) salts with gave: {[Fe2(L1)3](BF4)4, 1; [Fe2(L1)3](ClO4)4, 2; [Fe2(L1)3]Cl4, 3; [Fe2(L1)3](SO4)2, 4; [Fe2(L2)3](BF4)4, 5; [Fe2(L2)3]Cl4, 6; [Fe2(L3)3](BF4)4; 7; [Fe2(L3)3]Cl4, 8; and [Fe2(L3)3](SO4)2, 9, as determined by UV-Vis, IR and 1H NMR spectroscopy, electrospray mass spectrometry (ESMS) and elemental analyses. A UV-Vis complexometric titration experiment between L3 and Fe(BF4)2 established conclusively a [Fe2(L3)3]4+ product species. 1H NMR spectroscopy showed that the complexes exist as both rac-(helical) and meso-(non-helical) isomers in DMSO-d6 solution at 298 K. L1-L3 were designed such that following complexation, six amide hydrogen atoms would line an inter-strand intrahelical cavity of sufficient size to facilitate the binding of guest species within it. Indeed, ESMS studies showed characteristic peaks typical of complex-anion species in solution. Furthermore, 1H NMR titration experiments showed that anions bind within the intrahelical cavity as titration of 1, 5 and 7 with Bu4NCl showed significant downfield shifts in the amide and bipyridyl H6 proton resonances to yield a species of 1 : 2 host to guest stoichiometry. Moreover, addition of Bu4NCl to 1, 5 and 7 shifted the rac-/meso-species distribution from 1 : 2 in favour of the meso- to 100% in favour of the rac-isomer, showing that Cl- ions favour the formation of the triple helicate species in DMSO-d6 solution.