10.1021/jacs.5b02147.s001
Benjamin
E. Partridge
Benjamin
E.
Partridge
Pawaret Leowanawat
Pawaret
Leowanawat
Emad Aqad
Emad
Aqad
Mohammad R. Imam
Mohammad R.
Imam
Hao-Jan Sun
Hao-Jan
Sun
Mihai Peterca
Mihai
Peterca
Paul A. Heiney
Paul A.
Heiney
Robert Graf
Robert
Graf
Hans W. Spiess
Hans W.
Spiess
Xiangbing Zeng
Xiangbing
Zeng
Goran Ungar
Goran
Ungar
Virgil Percec
Virgil
Percec
Increasing
3D Supramolecular Order by Decreasing Molecular
Order. A Comparative Study of Helical Assemblies of Dendronized Nonchlorinated
and Tetrachlorinated Perylene Bisimides
American Chemical Society
2015
AB 3 minidendrons
semifluorinated dodecyl groups
2 EO
supramolecular
Cl 4PBI compounds
3 D order
3 D arrays
2 methylenic units
assembly
Tetrachlorinated Perylene BisimidesA nonplanar
hydrogenated
semifluorinated dendronized Cl 4PBI
3 D Supramolecular Order
Cl 4PBI
NMR
3 D crystals
2 D assemblies
tetrachlorinated perylene bisimide
2 D columnar
2015-04-22 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Increasing_3D_Supramolecular_Order_by_Decreasing_Molecular_Order_A_Comparative_Study_of_Helical_Assemblies_of_Dendronized_Nonchlorinated_and_Tetrachlorinated_Perylene_Bisimides/2174293
A nonplanar,
twisted, and flexible tetrachlorinated perylene bisimide
(Cl<sub>4</sub>PBI) was functionalized with two AB<sub>3</sub> minidendrons
containing hydrogenated or semifluorinated dodecyl groups. The hydrogenated
dendron was attached to the imide groups of Cl<sub>4</sub>PBI via <i>m</i> = 0, 1, and 2 methylenic units, whereas the dendron containing
semifluorinated groups was attached via <i>m</i> = 3 or
a diĀ(ethylene oxide) linker (<i>m</i> = 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 Cl<sub>4</sub>PBI containing hydrogenated
dendrons self-organize into exclusively 3D crystalline periodic arrays
under thermodynamic control for <i>m</i> = 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
Cl<sub>4</sub>PBI with <i>m</i> = 3 formed a 2D columnar
hexagonal array under kinetic control, whereas the compound with <i>m</i> = 2EO formed an unusual 2D honeycomb-like hexagonal phase
under thermodynamic control. These Cl<sub>4</sub>PBI 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.