TY - JOUR
T1 - Metal-Organic Self-Assembled Trefoil Knots for C - Br Bond Activation
AU - Prakasam, Thirumurugan
AU - Devaraj, Anthonisamy
AU - Saha, Rupak
AU - Lusi, Matteo
AU - Brandel, Jeremy
AU - Esteban-Gómez, David
AU - Platas-Iglesias, Carlos
AU - Olson, Mark Anthony
AU - Mukherjee, Partha Sarathi
AU - Trabolsi, Ali
N1 - Funding Information:
The research described here was sponsored by New York University Abu Dhabi, in the UAE. T.P and A.T thank NYUAD for its generous support for the research program at NYUAD. We would like to acknowledge the Al Jalila Foundation (AJF201646) for funding this research work. The authors also thank the Core Technology Platforms at NYUAD. P.S.M. thanks the Science and Engineering Research Board (New Delhi) for a research grant [Grant No. EMR/ 2015/002353]. A.D is thankful to UGC-New Dehli for Dr. D. S. Kothari postdoctoral fellowship. The authors thank Dr. Rana Bilbeisi for performing the titration experiment of bromide with Cd-TK by 1H NMR and determining the binding constants.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/3/1
Y1 - 2019/3/1
N2 - 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.
AB - 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.
KW - C-Br bond cleavage
KW - [C-H···anion] interactions
KW - anion receptors
KW - catalysis
KW - trefoil Knot
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U2 - 10.1021/acscatal.8b04650
DO - 10.1021/acscatal.8b04650
M3 - Article
AN - SCOPUS:85062426699
SN - 2155-5435
VL - 9
SP - 1907
EP - 1914
JO - ACS Catalysis
JF - ACS Catalysis
IS - 3
ER -