Exploitation of the menshutkin reaction for the controlled assembly of halogen bonded architectures incorporating 1,2-diiodotetrafluorobenzene and 1,3,5-Triiodotrifluorobenzene

Pfrunder, Michael, Micallef, Aaron, Rintoul, Llew, Arnold, Dennis, Davy, Karl, & McMurtrie, John (2012) Exploitation of the menshutkin reaction for the controlled assembly of halogen bonded architectures incorporating 1,2-diiodotetrafluorobenzene and 1,3,5-Triiodotrifluorobenzene. Crystal Growth and Design, 12(2), pp. 714-724.

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Abstract

1,4-Diazabicyclo[2.2.2]octane (DABCO) forms well-defined co-crystals with 1,2-diiodotetrafluorobenzene (1,2-DITFB), [(1,2-DITFB)2DABCO], and 1,3,5-triiodotrifluorobenzene, [(1,3,5-TITFB)2DABCO]. Both systems exhibited lower-than-expected supramolecular connectivity, which inspired a search for polymorphs in alternative crystallization solvents. In dichloromethane solution, the Menshutkin reaction was found to occur, generating chloride anions and quaternary ammonium cations through the reaction between the solvent and DABCO. The controlled in situ production of chloride ions facilitated the crystallization of new halogen bonded networks, DABCO–CH2Cl[(1,2-DITFB)Cl] (zigzag X-bonded chains) and (DABCO–CH2Cl)3[(1,3,5-TITFB)2Cl3]·CHCl3 (2D pseudo-trigonal X-bonded nets displaying Borremean entanglement), propagating with charge-assisted C–I···Cl– halogen bonds. The method was found to be versatile, and substitution of DABCO with triethylamine (TEA) gave (TEA-CH2Cl)3[(1,2-DITFB)Cl3]·4(H2O) (mixed halogen bond hydrogen bond network with 2D supramolecular connectivity) and TEA-CH2Cl[(1,3,5-TITFB)Cl] (tightly packed planar trigonal nets). The co-crystals were typically produced in high yield and purity with relatively predictable supramolecular topology, particularly with respect to the connectivity of the iodobenzene molecules. The potential to use this synthetic methodology for crystal engineering of halogen bonded architectures is demonstrated and discussed.

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ID Code: 77249
Item Type: Journal Article
Refereed: Yes
DOI: 10.1021/cg201017r
ISSN: 1528-7483
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > INORGANIC CHEMISTRY (030200)
Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600)
Australian and New Zealand Standard Research Classification > ENGINEERING (090000) > MATERIALS ENGINEERING (091200)
Divisions: Past > Schools > Chemistry
Past > QUT Faculties & Divisions > Faculty of Science and Technology
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 07 Oct 2014 07:04
Last Modified: 30 Nov 2015 00:39

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