title: Halogen bonding between an isoindoline nitroxide and 1,4-diiodotetrafluorobenzene: new tools and tectons for self-assembling organic spin systems.
abstract: Radical assembly: Halogen bonding has been observed for the first time between an isoindoline nitroxide and an iodoperfluorocarbon (see figure), which cocrystallize to form a discrete 2:1 supramolecular compound in which N--O(.)I halogen bonding is the dominant intermolecular interaction. This illustrates the potential use of halogen bonding and isoindoline nitroxide tectons for the assembly of organic spin systems.The isoindoline nitroxide 1,1,3,3-tetramethylisoindolin-2-yloxyl (TMIO) and 1,4-diiodotetrafluorobenzene readily form a discrete 2:1 complex that shows evidence of relatively strong N--O(.)I halogen bonding. This interaction was characterized in the solid state by single-crystal X-ray analysis, thermal analysis, and vibrational spectroscopy (IR and Raman), backed by density functional theory calculations. EPR spectroscopy performed on a solution of TMIO in pentafluoroiodobenzene, a halogen-bonding donor, indicates that halogen bonding induces an increase in electron density at the nitroxide nitrogen nucleus and an increase in the nitroxide rotational correlation time. Our findings demonstrate the potential of utilizing halogen-bonding interactions to promote the self-assembly of new isoindoline nitroxide tectons for the preparation of organic spin systems.
authors.affiliation: Centre for Magnetic Resonance, University of Queensland, St. Lucia, Queensland, Australia.
authors.forename: Graeme R
authors.initials: GR
authors.lastname: Hanson
authors.forename: Paul
authors.initials: P
authors.lastname: Jensen
authors.forename: John
authors.initials: J
authors.lastname: McMurtrie
authors.forename: Llew
authors.initials: L
authors.lastname: Rintoul
authors.forename: Aaron S
authors.initials: AS
authors.lastname: Micallef
mesh_terms: D000465:Algorithms; D001555:Benzene Derivatives / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003497:Cyclic N-Oxides / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D006846:Hydrocarbons, Halogenated / Q000138:chemical synthesis* / Q000737:chemistry; D054833:Isoindoles / Q000737:chemistry*; D008968:Molecular Conformation; D015394:Molecular Structure; D009589:Nitrogen Oxides / Q000737:chemistry; D013816:Thermodynamics
chemical_list: C540373:1,4-diiodotetrafluorobenzene; D001555:Benzene Derivatives; D003497:Cyclic N-Oxides; D006846:Hydrocarbons, Halogenated; D054833:Isoindoles; D009589:Nitrogen Oxides; C039900:nitroxyl