title: A supramolecular helix that disregards chirality.
abstract: The functions of complex crystalline systems derived from supramolecular biological and non-biological assemblies typically emerge from homochiral programmed primary structures via first principles involving secondary, tertiary and quaternary structures. In contrast, heterochiral and racemic compounds yield disordered crystals, amorphous solids or liquids. Here, we report the self-assembly of perylene bisimide derivatives in a supramolecular helix that in turn self-organizes in columnar hexagonal crystalline domains regardless of the enantiomeric purity of the perylene bisimide. We show that both homochiral and racemic perylene bisimide compounds, including a mixture of 21 diastereomers that cannot be deracemized at the molecular level, self-organize to form single-handed helical assemblies with identical single-crystal-like order. We propose that this high crystalline order is generated via a cogwheel mechanism that disregards the chirality of the self-assembling building blocks. We anticipate that this mechanism will facilitate access to previously inaccessible complex crystalline systems from racemic and homochiral building blocks.
authors.affiliation: Roy &Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Cécile
authors.identifier: http://orcid.org/0000-0003-0320-3498
authors.initials: C
authors.lastname: Roche
authors.affiliation: Roy &Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.|Department of Physics and Astronomy, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6396, USA.
authors.forename: Hao-Jan
authors.initials: HJ
authors.lastname: Sun
authors.affiliation: Roy &Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Pawaret
authors.initials: P
authors.lastname: Leowanawat
authors.affiliation: RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
authors.forename: Fumito
authors.identifier: http://orcid.org/0000-0002-9387-6081
authors.initials: F
authors.lastname: Araoka
authors.affiliation: Roy &Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Benjamin E
authors.identifier: http://orcid.org/0000-0003-2359-1280
authors.initials: BE
authors.lastname: Partridge
authors.affiliation: Roy &Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Mihai
authors.identifier: http://orcid.org/0000-0002-7247-4008
authors.initials: M
authors.lastname: Peterca
authors.affiliation: Roy &Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Daniela A
authors.initials: DA
authors.lastname: Wilson
authors.affiliation: Roy &Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Margaret E
authors.initials: ME
authors.lastname: Prendergast
authors.affiliation: Department of Physics and Astronomy, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6396, USA.
authors.forename: Paul A
authors.initials: PA
authors.lastname: Heiney
authors.affiliation: Max-Planck Institute for Polymer Research, Mainz 55128, Germany.
authors.forename: Robert
authors.initials: R
authors.lastname: Graf
authors.affiliation: Max-Planck Institute for Polymer Research, Mainz 55128, Germany.
authors.forename: Hans W
authors.initials: HW
authors.lastname: Spiess
authors.affiliation: Department of Materials Science and Engineering, University of Sheffield, Sheffield S1 3JD, UK.
authors.forename: Xiangbing
authors.initials: X
authors.lastname: Zeng
authors.affiliation: Department of Materials Science and Engineering, University of Sheffield, Sheffield S1 3JD, UK.|Department of Physics, Zhejiang Sci-Tech University, Hangzhou 310018, China.
authors.forename: Goran
authors.initials: G
authors.lastname: Ungar
authors.affiliation: Roy &Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Virgil
authors.initials: V
authors.lastname: Percec
mesh_terms: D002942:Circular Dichroism; D003460:Crystallization; D007094:Imides / Q000138:chemical synthesis* / Q000737:chemistry*; D046911:Macromolecular Substances; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010569:Perylene / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D044367:Phase Transition; D012996:Solutions; D013056:Spectrophotometry, Ultraviolet; D013237:Stereoisomerism; D014961:X-Ray Diffraction
chemical_list: D007094:Imides; D046911:Macromolecular Substances; D012996:Solutions; C510697:perylene bisimide; D010569:Perylene