Homochiral [2.2]Paracyclophane Self-Assembly Promoted by Transannular Hydrogen Bonding

[2.2]paracyclophane (pCp), unlike many π‐building blocks, has been virtually unexplored in supramolecular constructs. Reported here is the synthesis and characterization of the first pCp derivatives capable of programmed self‐assembly into extended cofacial π‐stacks in solution and the solid state....

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Bibliographic Details
Published in:Angewandte Chemie 2016-08, Vol.128 (36), p.10884-10889
Main Authors: Fagnani, Danielle E., Meese Jr, Michael J., Abboud, Khalil A., Castellano, Ronald K.
Format: Article
Language:English
Subjects:
Amides
Chemical bonds
Chemistry
Chirality
Chiralität
Construction
Crystallography
Cyclophane
Derivatives
Formations
Hydrogen bonding
Hydrogen bonds
Monomers
NMR
Nuclear magnetic resonance
Polymers
Selbstorganisation
Self assembly
Solid state
Stacks
Strands
Supramolekulare Chemie
Wasserstoffbrücken
X-ray crystallography
X-rays
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Summary:[2.2]paracyclophane (pCp), unlike many π‐building blocks, has been virtually unexplored in supramolecular constructs. Reported here is the synthesis and characterization of the first pCp derivatives capable of programmed self‐assembly into extended cofacial π‐stacks in solution and the solid state. The design employs transannular (intramolecular) hydrogen bonds (H‐bonds), hitherto unstudied in pCps, between pseudo‐ortho‐positioned amides of a pCp‐4,7,12,15‐tetracarboxamide (pCpTA) to preorganize the molecules for intermolecular H‐bonding with π‐stacked neighbors. X‐ray crystallography confirms the formation of homochiral, one‐dimensional pCpTA stacks helically laced with two H‐bond strands. The chiral sense is dictated by the planar chirality (Rp or Sp) of the pCpTA monomers. A combination of NMR, IR, and UV/Vis studies confirms the formation of the first supramolecular pCp polymers in solution. Molekularer Zwirn: [2.2]Paracyclophan(pCp)‐Derivate können durch programmierte Selbstorganisation in Lösung und im Festkörper große π‐Stapel bilden. Die eindimensionalen Strukturen sind homochiral und infolge einer Kombination von transannularen (intramolekularen) und intermolekularen Wasserstoffbrücken helikal verwunden. pCpTA=pCp‐4,7,12,15‐Tetracarboxamid.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201605286