title: Screening Libraries of Semifluorinated Arylene Bisimides to Discover and Predict Thermodynamically Controlled Helical Crystallization.
abstract: 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 AB3chiral 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 Cl4PBIs 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 Å π-π 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.
authors: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Ming-Shou
authors: MS
authors: Ho
authors: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Benjamin E
authors: BE
authors: Partridge
authors: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Hao-Jan
authors: HJ
authors: Sun
authors: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Dipankar
authors: D
authors: Sahoo
authors: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Pawaret
authors: P
authors: Leowanawat
authors: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.|Department of Physics and Astronomy, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6396, United States.
authors: Mihai
authors: M
authors: Peterca
authors: Max-Planck Institute for Polymer Research , 55128 Mainz, Germany.
authors: Robert
authors: R
authors: Graf
authors: Max-Planck Institute for Polymer Research , 55128 Mainz, Germany.
authors: Hans W
authors: HW
authors: Spiess
authors: Department of Materials Science and Engineering, University of Sheffield , Sheffield S1 3JD, United Kingdom.
authors: Xiangbing
authors: X
authors: Zeng
authors: Department of Materials Science and Engineering, University of Sheffield , Sheffield S1 3JD, United Kingdom.|Department of Physics, Zhejiang Sci-Tech University , Hangzhou 3110018, China.
authors: Goran
authors: G
authors: Ungar
authors: Department of Physics and Astronomy, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6396, United States.
authors: Paul A
authors: PA
authors: Heiney
authors: Department of Applied Chemistry, National Chiao Tung University , 1001 Ta Hsueh Road, Hsin-Chu 30049, Taiwan.
authors: Chain-Shu
authors: CS
authors: Hsu
authors: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Virgil
authors: V
authors: Percec
mesh_terms: D020650:Combinatorial Chemistry Techniques / Q000379:methods; D003460:Crystallization; D007094:Imides / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry*; D010569:Perylene / Q000737:chemistry*; D011084:Polycyclic Aromatic Hydrocarbons / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D007094:Imides; D009281:Naphthalenes; D011084:Polycyclic Aromatic Hydrocarbons; C031721:naphthalene; D010569:Perylene
keywords: helical crystallization; library; screening; semifluorinated arylene bisimides; structural analysis; thermodynamic control