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Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework.

ABSTRACT: Controlling chemical reactions by the supramolecular confinement effects of nanopores has attracted great attention. Here we show that open metal sites in porous coordination frameworks can constitute more powerful and strict templates for precision syntheses. A Fe(III) dicarboxylate framework functionalized with triangularly arranged metal sites is used to accomplish [2+2+2] cyclotrimerization reactions for organonitrile, alkyne and alkene monomers bearing a geometrically suitable pyridyl group. In situ single-crystal X-ray diffraction facilitates the direct observation of such a coordination templated reaction, before cylcotrimerization, the monomer coordinates at the Fe(III) centre by its pyridyl donor, which forces three unsaturated groups to gather around a position very similar with that of the desired covalent cyclic trimer. After the reaction, the trimers serve as tripodal ligands to perfectly fix the Fe(III) ions and the whole crystal to generate an exceptionally rigid and porous material with large surface area coupled with guest-proof zero thermal expansion.

SUBMITTER: Wei YS

PROVIDER: S-EPMC4595715 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

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Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework.

Wei Yong-Sheng YS Zhang Mei M Liao Pei-Qin PQ Lin Rui-Biao RB Li Tai-Yang TY Shao Guang G Zhang Jie-Peng JP Chen Xiao-Ming XM

Nature communications 20150918

Controlling chemical reactions by the supramolecular confinement effects of nanopores has attracted great attention. Here we show that open metal sites in porous coordination frameworks can constitute more powerful and strict templates for precision syntheses. A Fe(III) dicarboxylate framework functionalized with triangularly arranged metal sites is used to accomplish [2+2+2] cyclotrimerization reactions for organonitrile, alkyne and alkene monomers bearing a geometrically suitable pyridyl group ...[more]

PMID: 26384254

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Project description:In this study, a minimum-run resolution IV and central composite design have been developed to optimize tetracycline removal efficiency over mesoporous carbon derived from the metal-organic framework MIL-53 (Fe) as a self-sacrificial template. Firstly, minimum-run resolution IV, powered by the Design-Expert program, was used as an efficient and reliable screening study for investigating a set of seven factors, these were: tetracycline concentration (A: 5-15 mg/g), dose of mesoporous carbons (MPC) (B: 0.05-0.15 g/L), initial pH level (C: 2-10), contact time (D: 1-3 h), temperature (E: 20-40 °C), shaking speed (F: 150-250 rpm), and Na+ ionic strength (G: 10-90 mM) at both low (-1) and high (+1) levels, for investigation of the data ranges. The 20-trial model was analyzed and assessed by Analysis of Variance (ANOVA) data, and diagnostic plots (e.g., the Pareto chart, and half-normal and normal probability plots). Based on minimum-run resolution IV, three factors, including tetracycline concentration (A), dose of MPC (B), and initial pH (C), were selected to carry out the optimization study using a central composite design. The proposed quadratic model was found to be statistically significant at the 95% confidence level due to a low P-value (<0.05), high R2 (0.9078), and the AP ratio (11.4), along with an abundance of diagnostic plots (3D response surfaces, Cook's distance, Box-Cox, DFFITS, Leverage versus run, residuals versus runs, and actual versus predicted). Under response surface methodology-optimized conditions (e.g., tetracycline concentration of 1.9 mg/g, MPC dose of 0.15 g/L, and pH level of 3.9), the highest tetracycline removal efficiency via confirmation tests reached up to 98.0%-99.7%. Also, kinetic intraparticle diffusion and isotherm models were systematically studied to interpret how tetracycline molecules were absorbed on an MPC structure. In particular, the adsorption mechanisms including "electrostatic attraction" and "π-π interaction" were proposed.

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Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework.

Publications

Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework.

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