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fluorine benzene groups are substituted with the hydrogen
atoms (DimH, TriH, DimH[lowem]ZZ and TriH[lowem]ZZ),
the steric effect disappears. The polymer of [1,5] diazocine
prefers to the ring structure rather than the zigzag confor-
mation, as indicated by their relative energies.
(BS2009CL026) and Qingdao Agricultural University
Research Foundation (631222).
REFERENCES AND NOTES
With the increase of the degree of the polymer, the ring
structure changes to the helix conformation. We also per-
formed the calculations for hexamer of [1,5] diazocine to
verify the above conclusions. These optimizations were per-
formed at B3LYP/3-21G* level for this system with the con-
sideration of the computational consumption. The results
demonstrate that the zigzag structure is preferred for the
system with the fluorine benzene groups. While, the helix
conformation is lower in energy for the hydrogen substituted
hexamer. Therefore, the zigzag structure is preferred for the
systems with the fluorine benzene side chain owing to their
strong steric effect, and the helix conformation is more sta-
ble than the zigzag one for the hydrogen substituted sys-
tems. The calculations with functional theory method
support that compound PBDA-a preferred to display helix
conformation. Compounds PBDA-b with methoxylphenyl
group preferred to display zigzag conformation structures
like PBDA-F owing to their strong steric effect.
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Novel polydiazocines containing the diazocine unit has been
synthesized via one-pot polymerization, and their molecular
structures are confirmed by 13C NMR, IR and MALDI-TOF. Elec-
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mers have been investigated. The resulting polymers exhibit
good solvent solubility, enhanced thermal stability (Td 5% 5
350 ꢀC). The results of polymer calculations using the density
functional theory method reveal the methoxy-substituted poly-
mer PBDA-b prefers to display the zigzag conformation and
hydrogen-substituted polymer PBDA-a prefers to display the
helix conformation structure. The new polydiazocines with
excellent thermal stability may have potential application as
molecular actuator and other organic electronic devices.
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ACKNOWLEDGMENTS
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We appreciate the financial support from NSFC (21174157),
Natural Sciences Foundation of Shandong Province
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