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Increasing 3D Supramolecular Order by Decreasing Molecular Order. A Comparative Study of Helical Assemblies of Dendronized Nonchlorinated and Tetrachlorinated Perylene Bisimides
journal contribution
posted on 2015-04-22, 00:00 authored by Benjamin
E. Partridge, Pawaret Leowanawat, Emad Aqad, Mohammad R. Imam, Hao-Jan Sun, Mihai Peterca, Paul A. Heiney, Robert Graf, Hans W. Spiess, Xiangbing Zeng, Goran Ungar, Virgil PercecA nonplanar,
twisted, and flexible tetrachlorinated perylene bisimide
(Cl4PBI) was functionalized with two AB3 minidendrons
containing hydrogenated or semifluorinated dodecyl groups. The hydrogenated
dendron was attached to the imide groups of Cl4PBI via m = 0, 1, and 2 methylenic units, whereas the dendron containing
semifluorinated groups was attached via m = 3 or
a di(ethylene oxide) linker (m = 2EO). The supramolecular
structures of these compounds, determined by a combination of differential
scanning calorimetry, X-ray diffraction, and solid-state NMR, were
compared with those of nonchlorinated planar and rigid PBI reported
previously, which demonstrated the thermodynamically controlled formation
of 2D periodic arrays at high temperatures and 3D arrays at low temperatures.
The molecularly less ordered Cl4PBI containing hydrogenated
dendrons self-organize into exclusively 3D crystalline periodic arrays
under thermodynamic control for m = 0 and 2, while
the more highly molecularly ordered PBI produced less stable and ordered
3D crystals and also 2D assemblies. This induction of a higher degree
of 3D order in supramolecular assemblies of the less well-ordered
molecular building blocks was unanticipated. The semifluorinated dendronized
Cl4PBI with m = 3 formed a 2D columnar
hexagonal array under kinetic control, whereas the compound with m = 2EO formed an unusual 2D honeycomb-like hexagonal phase
under thermodynamic control. These Cl4PBI compounds provide
a new route to stable crystalline assemblies via thermodynamic control
at lower temperatures than previously obtained with PBI, thus generating
3D order in an accessible range of temperature of interest for structural
analysis and for technological applications.
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AB 3 minidendronssemifluorinated dodecyl groups2 EOsupramolecularCl 4PBI compounds3 D order3 D arrays2 methylenic unitsassemblyTetrachlorinated Perylene BisimidesA nonplanarhydrogenatedsemifluorinated dendronized Cl 4PBI3 D Supramolecular OrderCl 4PBINMR3 D crystals2 D assembliestetrachlorinated perylene bisimide2 D columnar
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