Cooperative binding in a phosphine oxide-based halogen bonded dimer drives supramolecular oligomerization
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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 by 31P NMR spectroscopy in d8-toluene solution, 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 d8-toluene and, surprisingly, d2-DCM into 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 d2-DCM solution, through halogen bonding, forming oligomeric assemblies.
Maugeri , L , Lebl , T , Cordes , D B , Slawin , A M Z & Philp , D 2017 , ' Cooperative binding in a phosphine oxide-based halogen bonded dimer drives supramolecular oligomerization ' Journal of Organic Chemistry , vol 82 , no. 4 , pp. 1986–1995 . DOI: 10.1021/acs.joc.6b02822
Journal of Organic Chemistry
Copyright © 2017 American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1021/acs.joc.6b02822
The authors thank the Marie Curie Initial Training Network on Replication and Adaption in Networks (ReAd) for financial support (early stage researcher funding to L.M.).
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