TY - JOUR
T1 - Cooperative Binding in a Phosphine Oxide-Based Halogen Bonded Dimer Drives Supramolecular Oligomerization
AU - Maugeri, Leonardo
AU - Lébl, Tomáš
AU - Cordes, David B.
AU - Slawin, Alexandra M.Z.
AU - Philp, Douglas
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/2/17
Y1 - 2017/2/17
N2 - 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 toluene-d8 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 toluene-d8 and, surprisingly, DCM-d2 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 DCM-d2 solution, through halogen bonding, forming oligomeric assemblies.
AB - 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 toluene-d8 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 toluene-d8 and, surprisingly, DCM-d2 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 DCM-d2 solution, through halogen bonding, forming oligomeric assemblies.
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U2 - 10.1021/acs.joc.6b02822
DO - 10.1021/acs.joc.6b02822
M3 - Article
C2 - 28107017
AN - SCOPUS:85013155683
SN - 0022-3263
VL - 82
SP - 1986
EP - 1995
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 4
ER -