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

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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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