Metal-Organic Self-Assembled Trefoil Knots for C - Br Bond Activation

Thirumurugan Prakasam, Anthonisamy Devaraj, Rupak Saha, Matteo Lusi, Jeremy Brandel, David Esteban-Gómez, Carlos Platas-Iglesias, Mark Anthony Olson, Partha Sarathi Mukherjee, Ali Trabolsi

    Research output: Contribution to journalArticle

    Abstract

    Synthesizing molecular knots that mimic the catalytic functionality of stereospecific or stereoselective enzymes are an intriguing task in chemistry. Synthetic anion receptors even with moderate halide binding affinities may catalyze chemical reactions involving carbon-halogen bond cleavage. Herein we report isostructural self-assembled trefoil molecular knots (Cu-TK, Cd-TK, Zn-TK) based on Cu(II), Cd(II), and Zn(II) that are capable of binding and stabilizing bromide within their central cavity and are capable of catalyzing C-Br bond cleavage. We also describe the role of noncovalent interactions between the knots and bromide as well as the size and shape of the knots on their catalytic efficiency. Among the studied three knots, Cu-TK was found to be more effective than Zn-TK and Cd-TK in catalyzing C-Br bond cleavage. The catalytic efficiency of the knots toward C-Br bond cleavage was found to be related to a balance between their attractive electrostatic interactions with bromide as well as cavity size and shape of the knots.

    Original languageEnglish (US)
    Pages (from-to)1907-1914
    Number of pages8
    JournalACS Catalysis
    Volume9
    Issue number3
    DOIs
    StatePublished - Mar 1 2019

    Fingerprint

    Bromides
    Metals
    Chemical activation
    Coulomb interactions
    Chemical reactions
    Halogens
    Negative ions
    Enzymes
    Carbon
    Anions

    Keywords

    • anion receptors
    • C-Br bond cleavage
    • catalysis
    • trefoil Knot
    • [C-H···anion] interactions

    ASJC Scopus subject areas

    • Catalysis
    • Chemistry(all)

    Cite this

    Prakasam, T., Devaraj, A., Saha, R., Lusi, M., Brandel, J., Esteban-Gómez, D., ... Trabolsi, A. (2019). Metal-Organic Self-Assembled Trefoil Knots for C - Br Bond Activation. ACS Catalysis, 9(3), 1907-1914. https://doi.org/10.1021/acscatal.8b04650

    Metal-Organic Self-Assembled Trefoil Knots for C - Br Bond Activation. / Prakasam, Thirumurugan; Devaraj, Anthonisamy; Saha, Rupak; Lusi, Matteo; Brandel, Jeremy; Esteban-Gómez, David; Platas-Iglesias, Carlos; Olson, Mark Anthony; Mukherjee, Partha Sarathi; Trabolsi, Ali.

    In: ACS Catalysis, Vol. 9, No. 3, 01.03.2019, p. 1907-1914.

    Research output: Contribution to journalArticle

    Prakasam, T, Devaraj, A, Saha, R, Lusi, M, Brandel, J, Esteban-Gómez, D, Platas-Iglesias, C, Olson, MA, Mukherjee, PS & Trabolsi, A 2019, 'Metal-Organic Self-Assembled Trefoil Knots for C - Br Bond Activation', ACS Catalysis, vol. 9, no. 3, pp. 1907-1914. https://doi.org/10.1021/acscatal.8b04650
    Prakasam T, Devaraj A, Saha R, Lusi M, Brandel J, Esteban-Gómez D et al. Metal-Organic Self-Assembled Trefoil Knots for C - Br Bond Activation. ACS Catalysis. 2019 Mar 1;9(3):1907-1914. https://doi.org/10.1021/acscatal.8b04650
    Prakasam, Thirumurugan ; Devaraj, Anthonisamy ; Saha, Rupak ; Lusi, Matteo ; Brandel, Jeremy ; Esteban-Gómez, David ; Platas-Iglesias, Carlos ; Olson, Mark Anthony ; Mukherjee, Partha Sarathi ; Trabolsi, Ali. / Metal-Organic Self-Assembled Trefoil Knots for C - Br Bond Activation. In: ACS Catalysis. 2019 ; Vol. 9, No. 3. pp. 1907-1914.
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