Superlative scaffold of 1,2,4-triazole derivative of glycine steering linear chain to a chiral helicate

M.M. Dirtu, A.D. Naik, J. Marchand-Brynaert, Y. Garcia, François Robert, C. Neuhausen, A. Léonard, B.-L. Su

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    Solvothermal and classical synthesis with an identical recipe involving 4H-1,2,4-triazol-4-yl acetic acid (HL1) and CdCl afforded two-dimensional (2D) (1) and one-dimensional (2) coordination polymers, respectively. Hexagonal plate-like crystals of [Cd (L1) Cl ] (1), which crystallize in the chiral orthorhombic space group (P2 2 2 ), were obtained in high yield. The 1,2,4-triazole-4-yl acetate (L1) ligand, which has a significant kink in the spacer, leads to the formation of a Cd complex displaying a 2D single-stranded helical array. The pitch height of the helix is equal to the length of the crystallographic a axis (7.579 Å) which comprises two cadmium atoms and two ligands. Solid-state emission of 1 shows a strong emission band around 465 nm with photoexcitation at 290 nm. Mercury porosimetry measurements reveal pore size distribution with a diameter of 80, 10, and 1 μm. BET shows no preference for N but a low H adsorption of 4 cm /g. Complex 1, which is constituted by a "soft" nonaromatic network that begins to collapse around 170 °C, was subjected to controlled pyrolysis to produce CdO with morphology and phase selectivity. Texture of the thus obtained pure cubic phase of CdO (β-form) was further tuned with the regulation of the annealing temperature. Crystals of rectangular blocks of [Cd(HL1L1)Cl]·2H O (2), which were formed in small quantity, feature a centrosymmetric, monoclinic space group (P2 /c). Their crystal structure reveals a one-dimensional linear chain where Cd atoms are connected by a triple bridge made up of one μ-chloride and two μ-N1,N2-1,2,4-triazole HL1 and L1. The coordination polymer charge is balanced by both chloride and the carboxylate group of L1.(Figure Presented)
    Original languageEnglish
    Pages (from-to)1375-1384
    Number of pages10
    JournalCrystal Growth and Design
    Issue number4
    Publication statusPublished - 6 Apr 2011


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