DNA has a structural basis to array functionalized building blocks. Here we report the synthesis of a series of artificial oligonucleotides, d(5'-GH(n)C-3') (n = 1 to 5), with hydroxypyridone nucleobases (H) as flat bidentate ligands. Right-handed double helices of the oligonucleotides, nCu2+.d(5'-GH(n)C-3')2 (n = 1 to 5), were quantitatively formed through copper ion (Cu2+)-mediated alternative base pairing (H-Cu2+-H), where the Cu2+ ions incorporated into each complex were aligned along the helix axes inside the duplexes with the Cu2+-Cu2+ distance of 3.7 +/- 0.1 angstroms. The Cu2+ ions were coupled ferromagnetically with one another through unpaired d electrons to form magnetic chains.
Over the past few decades, supramolecular chirality in discrete metallosupramolecular architectures has received considerable attention. In this review, a comprehensive summary of discrete, chiral coordination-driven structures, including helices, metallacycles, metallocages, etc., is presented. Although chirality can be introduced prior to, during or even after the coordination self-assembly process, this review puts major emphasis on the more recent development of metallosupramolecular architectures from chiral components, where chirality arises from the enantiopure or racemic scaffolds (bridging or auxiliary ligand). Special attention will be paid to homochiral metallo-assemblies using achiral components where chirality is obtained as a consequence of the twisting of the ligands. Additionally, the potential applications of homochiral metallosupramolecular architectures are also discussed. We hope that this review will be of interest to researchers attempting to design new elaborate homochiral metallosupramolecular architectures with even greater complexity and potential for functions such as chiral recognition, enantiomer separation, asymmetric catalysis, nonlinear sensors, and devices.
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