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Macrocyclic Diacetylene–Terthiophene Cocrystal: Molecular Self-Assembly, Topochemical Polymerization, and Energy Transfer
journal contribution
posted on 2019-12-12, 13:50 authored by Kwangmin Bae, Jung-Moo Heo, Mohammed Iqbal Khazi, Joonyoung Francis Joung, Sungnam Park, Youngmee Kim, Jong-Man KimThe macrocyclic structure offers direction-control self-assembly
to generate columnar supramolecular architectures with a guest molecule-accessible
interior cavity. Owing to the π–π stacking characteristic
and photopolymerizable feature of the diacetylenic template, macrocyclic
diacetylenes (MCDAs) have emerged as an intriguing molecular design
for constructing arrays of covalently connected nanochannels. The
energy transfer mechanism by engineering host–guest cocrystals
of self-assembling π-electron-rich motifs has been widely accepted
for devising organic electronics. A highly fluorescent and polymerizable
cocrystal of macrocyclic diacetylene-terthiophene (MCDA-3T) was constructed. Single-crystal X-ray diffraction analysis reveals
well-ordered columnar assembly of MCDA with stacking geometry close-to-ideal
packing parameters preferred for the topochemical polymerization.
Inspection of the extended crystal packing pattern and by elemental
analysis confirms the inclusion of the 3T guest in outer-space positioned
along the parallel-packed MCDA columns, resulting in an array of nanochannels.
UV-induced polymerization of MCDA-3T cocrystal transforms
into covalently cross-linked PDAs and displays Förster resonance
energy transfer behavior between fluorescent 3T and conjugated PDA
polymer. The energy transfer phenomenon observed with the tubular
PDA and oligothiophenes should be useful in the design of new energy
harvesting functional supramolecules.
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diacetylenic templateself-assembling π- electron-rich motifsphotopolymerizable featureenergy transfer phenomenonenergy transfer mechanismmacrocyclic diacetylene-terthiopheneMCDA -3T cocrystalguest molecule-accessible3 T guestSingle-crystal X-ray diffraction analysistopochemical polymerizationMolecular Self-Assemblywell-ordered columnar assemblyenergy harvestingarrayparallel-packed MCDA columnscolumnar supramolecular architecturesmacrocyclic structureUV-induced polymerization3 TMCDA -3Tcovalently cross-linked PDAsEnergy Transfermacrocyclic diacetylenesdirection-control self-assemblyTopochemical PolymerizationnanochannelPDA polymergeometry close-to-idealpolymerizable cocrystal
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