The versatile, efficient, and stereoselective self-assembly of transition-metal helicates by using hydrogen-bonds

A diverse range of dinuclear double-stranded helicates in which the ligand strand is built up by using hydrogen-bonding has been synthesized. The helicates, formulated as [Co(2)(L)(2)(L-H)(2)X(2)], readily self-assemble from a mixture of a suitable pyridine-alcohol compound (L; for example, 6-methylpyridine-2-methanol, 1), and a CoX(2) salt in the presence of base. Nine such helicates have been characterized by X-ray crystallography. For helicates derived from the same pyridine-alcohol precursor, a remarkable regularity was found for both the molecular structure and the crystal packing arrangements, regardless of the nature of the ancillary ligand (X). A notable exception was observed in the solid-state structure of [Co(2)(1)(2)(1-H)(2)(NCS)(2)] for which intermolecular nonbonded contacts between the sulfur atoms (SS=3.21 A) lead to the formation of 1D chains. Helicates derived from (R)-6-methylpyridine-2-methanol (2) are soluble in solvents such as CH(3)CN and CH(2)Cl(2), and their self-assembly could be monitored in solution by (1)H NMR, UV/Vis, and CD titrations. No intermediate complexes were observed to form in a significant concentration at any point throughout these titrations. The global thermodynamic stability constant of [Co(2)(2)(2)(2-H)(2)(NO(3))(2)] was calculated from spectrophotometric data to be logbeta=8.9(8). The stereoisomerism of these helicates was studied in some detail and the self-assembly process was found to be highly stereoselective. The chirality of the ligand precursors can control the absolute configuration of the metal centers and thus the overall helicity of the dinuclear assemblies. Furthermore, the enantiomers of rac-6-methylpyridine-2-methanol (3) undergo a self-recognition process to form exclusively homochiral helicates in which the four pyridine-alcohol units possess the same chirality.