Complementary,Cooperative Ditopic Halogen Bonding and Electron Donor-Acceptor π-π Complexation in the Formation of Cocrystals |
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Authors: | Erin D. Speetzen Chideraa I. Nwachukwu Nathan P. Bowling Eric Bosch |
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Affiliation: | 1.Department of Chemistry, University of Wisconsin-Stevens Point, 2101 South Avenue, Stevens Point, WI 54481, USA; (E.D.S.); (N.P.B.);2.Chemistry Department, Missouri State University, 901 South National Avenue, Springfield, MO 65897, USA; |
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Abstract: | This study expands and combines concepts from two of our earlier studies. One study reported the complementary halogen bonding and π-π charge transfer complexation observed between isomeric electron rich 4-N,N-dimethylaminophenylethynylpyridines and the electron poor halogen bond donor, 1-(3,5-dinitrophenylethynyl)-2,3,5,6-tetrafluoro-4-iodobenzene while the second study elaborated the ditopic halogen bonding of activated pyrimidines. Leveraging our understanding on the combination of these non-covalent interactions, we describe cocrystallization featuring ditopic halogen bonding and π-stacking. Specifically, red cocrystals are formed between the ditopic electron poor halogen bond donor 1-(3,5-dinitrophenylethynyl)-2,4,6-triflouro-3,5-diiodobenzene and each of electron rich pyrimidines 2- and 5-(4-N,N-dimethyl-aminophenylethynyl)pyrimidine. The X-ray single crystal structures of these cocrystals are described in terms of halogen bonding and electron donor-acceptor π-complexation. Computations confirm that the donor-acceptor π-stacking interactions are consistently stronger than the halogen bonding interactions and that there is cooperativity between π-stacking and halogen bonding in the crystals. |
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Keywords: | ditopic halogen bonding electron donor acceptor complexation pi-stacking cooperative halogen bonding and electron donor acceptor complexation complementary halogen bonding and electron donor acceptor complexation charge-transfer complexation tetrel bonding |
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