TY - JOUR
T1 - Macrocyclic Diacetylene-Terthiophene Cocrystal
T2 - Molecular Self-Assembly, Topochemical Polymerization, and Energy Transfer
AU - Bae, Kwangmin
AU - Heo, Jung Moo
AU - Khazi, Mohammed Iqbal
AU - Joung, Joonyoung Francis
AU - Park, Sungnam
AU - Kim, Youngmee
AU - Kim, Jong Man
N1 - Funding Information:
This investigation was supported financially by a National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (NRF-2017R1A2A1A05000752).
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2020/1/2
Y1 - 2020/1/2
N2 - The macrocyclic structure offers direction-control self-assembly to generate columnar supramolecular architectures with a guest molecule-accessible interior cavity. Owing to the π-πstacking 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.
AB - The macrocyclic structure offers direction-control self-assembly to generate columnar supramolecular architectures with a guest molecule-accessible interior cavity. Owing to the π-πstacking 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.
UR - http://www.scopus.com/inward/record.url?scp=85076780562&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.9b01351
DO - 10.1021/acs.cgd.9b01351
M3 - Article
AN - SCOPUS:85076780562
VL - 20
SP - 434
EP - 441
JO - Crystal Growth and Design
JF - Crystal Growth and Design
SN - 1528-7483
IS - 1
ER -