An investigation of the self-assembly of neutral, interlaced, triple-stranded molecular braids

摘要

The synthesis and structures of six compounds prepared in two different systems have been explored with the purpose of isolating coordination polymers with interlaced triple-stranded molecular braid architectures. The dinuclear paddle-wheel units of [Cu-2-(maa)(4)center dot 2H(2)O] can be rationally tuned to form three classes of isomorphous compounds, namely [Cu-2(maa)(4)(bpp)] (1) (bpp = 1,3-bis(4-pyridyl)propane, Hmaa = 2-methylacrylic acid), [Cu-3(maa)(6)(bpp)(2)] (2), and [Cu-4(maa)(8)(bpp)(4)(H2O)(2)]center dot 2H(2)O (3), with a bridging bpp ligand, at controlled ligand-to-metal molar ratios, and lead to three coordination polymers having similar one-dimensional characteristics but different mono- and dinuclear nodes. Compound 1, with a bpp:[Cu-2-(maa)(4)center dot 2H(2)O] stoichiometry of 1:1, contains a zigzag chain containing dinuclear nodes, whereas polymer 2, with a bpp:[Cu-2(maa)(4)center dot 2H(2)O] stoichiometry of 1.5:1, also adopts the topology of a zigzag chain but with both mono- and dinuclear nodes. Compound 3, with a bpp:[Cu-2(maa)(4)center dot 2H(2)O] stoichiometry of 2:1, contains a neutral, interlaced, triple-stranded molecular braid, which is interwoven by three single-stranded meso-helical chains that contain only a mononuclear node. With the three aromatic chelating terminal ligands 2,2':6',2"-terpyridine (tpy), 1,10-phenanthroline (phen), and di(2-pyridyl)amine (dpa) we have also prepared three neutral complexes containing the linear, rigid bridging ligand biphenyl-4,4'-dicarboxylate (bpdc), namely [Cd(bpdc)(tpy)]center dot H2O (4), [Cu(bpdc)(phen)(2)]center dot 4.25H(2)O (5), and [Cu(bpdc)(dpa)] (6). An infinite meso-helix is formed initially in 4, and then three of these chains assemble into a triple-stranded braid similar to that of 3. Complexes 5 and 6 have a mononuclear and a looped dinuclear structure, respectively. Compounds 3 and 4 are unusual examples of triple-stranded molecular braid coordination frameworks based on different types of co-ligands.