Influence of water content on the self-assembly of metal-organic frameworks based on pyridine-3,5-dicarboxylate.

A 0D discrete molecule [Co(3,5-pdc)(H2O)5].2H2O (1) was obtained in quantitative yield from the reaction of CoCl2.6H2O and pyridine-3,5-dicarboxylate (3,5-pdc) in pure water solvent at ambient temperature. While a 1D zigzag chain species, [{Co(3,5-pdc)(H2O)4}.H2O]n (2), was produced in a water-rich environment, a 2D layer compound, [Co(3,5-pdc)(H2O)2]n (3), with a 6(3) topology was generated under a water-reduced condition and a 2D sheet structure, [{Cu(3,5-pdc)(py)2}.H2O.EtOH]n (4), was formed under a water-poor condition. Compounds 1, 2, and 4 were characterized by single-crystal X-ray diffraction analysis. The 1D zigzag chain 2 shows a recoverable collapsing property. Compound 4 adopts a 2D sheet structure with a 4.8(2) topology, observed for the first time for the 3,5-pdc-related metal-organic frameworks. Water content was found to be an important factor in determining the topologies of the products in the self-assembly of divalent metal ions (Co2+, Cu2+) and pyridine-3,5-dicarboxylate under mild conditions.

Proton NMR studies of 5'-d-(TC)(3) (CT)(3) (AG)(3)-3'--a paperclip triplex: the structural relevance of turns.

In this study, we present the results of structural analysis of an 18-mer DNA 5'-T(1)C(2)T(3)C(4)T(5)C(6)C(7)T(8)C(9)T(10)C(11)T(12)A(13)G(14)A(15)G(16)A(17)G(18)-3' by proton nuclear magnetic resonance (NMR) spectroscopy and molecular modeling. The NMR data are consistent with characteristics for triple helical structures of DNA: downfield shifting of resonance signals, typical for the H3(+) resonances of Hoogsteen-paired cytosines; pH dependence of these H3(+) resonance; and observed nuclear Overhauser effects consistent with Hoogsteen and Watson-Crick basepairing. A three-dimensional model for the triplex is developed based on data obtained from two-dimensional NMR studies and molecular modeling. We find that this DNA forms an intramolecular "paperclip" pyrimidine-purine-pyrimidine triple helix. The central triads resemble typical Hoogsteen and Watson-Crick basepairing. The triads at each end region can be viewed as hairpin turns stabilized by a third base. One of these turns is comprised of a hairpin turn in the Watson-Crick basepairing portion of the 18-mer with the third base coming from the Hoogsteen pairing strand. The other turn is comprised of two bases from the continuous pyrimidine portion of the 18-mer, stabilized by a hydrogen-bond from a purine. This "triad" has well defined structure as indicated by the number of nuclear Overhauser effects and is shown to play a critical role in stabilizing triplex formation of the internal triads.