標題: Screening Libraries of Semifluorinated Arylene Bisimides to Discover and Predict Thermodynamically Controlled Helical Crystallization
作者: Ho, Ming-Shou
Partridge, Benjamin E.
Sun, Hao-Jan
Sahoo, Dipankar
Leowanawat, Pawaret
Peterca, Mihai
Graf, Robert
Spiess, Hans W.
Zeng, Xiangbing
Ungar, Goran
Heiney, Paul A.
Hsu, Chain-Shu
Percec, Virgil
應用化學系
Department of Applied Chemistry
關鍵字: semifluorinated arylene bisimides;library;screening;thermodynamic control;helical crystallization;structural analysis
公開日期: 十二月-2016
摘要: Synthesis, structural, and retrostructural analysis of a library containing 16 self-assembling perylene (PBI), 1,6,7,12-tetrachloroperylene (Cl4PBI), naphthalene (NBI), and pyromellitic (PMBI) bisimides functionalized with environmentally friendly AB(3) chiral racemic semifluorinated minidendrons at their imide groups via m = 0, 1, 2, and 3 methylene units is reported. These semifluorinated compounds melt at lower temperatures than homologous hydrogenated compounds, permitting screening of all their thermotropic phases via structural analysis to discover thermodynamically controlled helical crystallization from propeller-like, cogwheel, and tilted molecules as well as lamellar-like structures. Thermodynamically controlled helical crystallization was discovered for propeller-like PBI, Cl4PBI and NBI with m = 0. Unexpectedly, assemblies of twisted Cl(4)PBIs exhibit higher order than those of planar PBIs. PBI with m = 1, 2, and 3 form a thermodynamically controlled columnar hexagonal 2D lattice of tilted helical columns with intracolumnar order. PBI and Cl4PBI with m = 1 crystallize via a recently discovered helical cogwheel mechanism, while NBI and PMBI with m = 1 form tilted helical columns. PBI, NBI and PMBI with m = 2 generate lamellar-like structures. 3D and 2D assemblies of PBI with m = 1, 2, and 3, NBI with m = 1 and PMBI with m = 2 exhibit 3.4 angstrom pi-pi stacking. The library approach applied here and in previous work enabled the discovery of six assemblies which self-organize via thermodynamic control into 3D and 2D periodic arrays, and provides molecular principles to predict the supramolecular structure of electronically active components.
URI: http://dx.doi.org/10.1021/acscombsci.6b00143
http://hdl.handle.net/11536/132751
ISSN: 2156-8952
DOI: 10.1021/acscombsci.6b00143
期刊: ACS COMBINATORIAL SCIENCE
Volume: 18
Issue: 12
起始頁: 723
結束頁: 739
顯示於類別:期刊論文