title: Cooperative Binding in a Phosphine Oxide-Based Halogen Bonded Dimer Drives Supramolecular Oligomerization.
abstract: Triphenylphosphine oxide forms halogen-bonded (XB) complexes with pentafluoroiodobenzene and a 1,4-diaryl-5-iodotriazole. The stability of these complexes is assessed computationally and by31P NMR spectroscopy in toluene-d8solution, where both complexes are weakly associated. This knowledge is applied to the design and synthesis of two self-complementary phosphine oxide-iodotriazole hybrids that incorporate a phosphine oxide XB acceptor and a 1,4-diphenyl-5-iodotriazole XB donor within the same molecule. The self-complementary design of these modules facilitates their assembly in both toluene-d8and, surprisingly, DCM-d2into dimers, with significant stabilities, through the formation of halogen-bonded diads. The stability of these assemblies is a result of significant levels of cooperative binding that is present in both solvents. The connection of two of these hybrid units together, using a flexible spacer, facilitates the aggregation of these modules in DCM-d2solution, through halogen bonding, forming oligomeric assemblies.
authors.affiliation: EaStChem and School of Chemistry, University of St Andrews , North Haugh, St Andrews KY16 9ST, United Kingdom.
authors.forename: Leonardo
authors.initials: L
authors.lastname: Maugeri
authors.affiliation: EaStChem and School of Chemistry, University of St Andrews , North Haugh, St Andrews KY16 9ST, United Kingdom.
authors.forename: Tomáš
authors.initials: T
authors.lastname: Lébl
authors.affiliation: EaStChem and School of Chemistry, University of St Andrews , North Haugh, St Andrews KY16 9ST, United Kingdom.
authors.forename: David B
authors.identifier: 0000-0002-5366-9168
authors.initials: DB
authors.lastname: Cordes
authors.affiliation: EaStChem and School of Chemistry, University of St Andrews , North Haugh, St Andrews KY16 9ST, United Kingdom.
authors.forename: Alexandra M Z
authors.initials: AM
authors.lastname: Slawin
authors.affiliation: EaStChem and School of Chemistry, University of St Andrews , North Haugh, St Andrews KY16 9ST, United Kingdom.
authors.forename: Douglas
authors.identifier: 0000-0002-9198-4302
authors.initials: D
authors.lastname: Philp