Macromolecules
Article
CuI (5 mol %), toluene (20 mL), and diisopropylamine (4 mL). The
reaction vessel was sealed and heated at 85 °C for 3 days upon which
the reaction mixture was filtered and concentrated. The residue was
repetitively precipitated from THF by dropwise addition to methanol,
hexane, and then methanol to give the final polymer solid.
General Procedure for Cyclopentannulation of Poly(arylene
ethynylene)s. In a glovebox were combined 3 (0.5 mmol),
poly(arylene ethynylene) (0.1 mmol), Pd2(dba)3 (0.01 mmol), P(o-
Tol)3 (0.01 mmol), KOAc (17 mmol), LiCl (0.1 mmol), and toluene/
DMF (5 mL/5 mL). The reaction vessel was sealed and heated at 130
°C for 6 days. The reaction mixture was filtered and concentrated. The
concentrated residue was repetitively precipitated from THF by
dropwise addition to methanol, hexane, and then methanol to give the
final polymer solid.
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COMPUTATIONAL METHODS
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All atom MD simulations were carried out within LAMMPS36 on
10mer oligomers of polymers 4 and 7. These oligomers were
simulated in 5000 explicit THF molecules using the OPLS-AA force
field,37 which has been applied to recent studies of conjugated
polymers and other oligomers.18,38,39 Because appropriate charges for
the fluorene nucleus were lacking, we optimized the geometry of this
nucleus using HF calculations with a 3-21G* basis set (since OPLS is
parametrized at the HF theory level,37,40 and assigned Mulliken
charges based on the results. HF calculations were performed using
Gaussian [03].40 The simulation box was set up initially as a 100 Å
cube, and NVT simulations were run at 400 K for 0.5 ns to relieve
unphysical contacts between the solvent and the oligomer. After 0.5
ns, a configuration was harvested every 0.1 ns for an additional 0.5 ns,
providing 5 starting configurations. Using these configurations, five
new NPT simulations were run for 3.5 ns at 300 K and a pressure of 1
atm. Densities converged by 2.5 ns for all 10 trials (5 of oligomer 4
and 5 of oligomer 7), and the data presented here was collected every
1 ps during the last ns of the simulation. All calculations were carried
out on the Rivanna cluster at The University of Virginia.
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ASSOCIATED CONTENT
* Supporting Information
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̈
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S
2011, 17 (45), 12756−12762.
(20) Liu, E.-C.; Chen, M.-K.; Li, J.-Y.; Wu, Y.-T. Chem. - Eur. J. 2015,
21 (12), 4755−4761.
(21) Bheemireddy, S. R.; Ubaldo, P. C.; Rose, P. W.; Finke, A. D.;
Zhuang, J.; Wang, L.; Plunkett, K. N. Angew. Chem., Int. Ed. 2015,
The Supporting Information is available free of charge on the
Detailed experimental procedures and NMR character-
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AUTHOR INFORMATION
Corresponding Authors
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(24) Wood, J. D.; Jellison, J. L.; Finke, A. D.; Wang, L.; Plunkett, K.
N. J. Am. Chem. Soc. 2012, 134 (38), 15783−15789.
(25) Lee, C.-H.; Plunkett, K. N. Org. Lett. 2013, 15 (6), 1202−1205.
(26) Jellison, J. L.; Lee, C.-H.; Zhu, X.; Wood, J. D.; Plunkett, K. N.
Angew. Chem., Int. Ed. 2012, 51, 12321−12324.
(27) Jin, T.; Zhao, J.; Asao, N.; Yamamoto, Y. Chem. - Eur. J. 2014, 20
(13), 3554−3576.
Present Address
§College of Chemistry and Molecular Engineering, Zhengzhou
University, Zhengzhou, China
Notes
(28) Theato, P.; Klok, H.-A. Functional Polymers by Post-Polymer-
ization Modification: Concepts, Guidelines and Applications; John Wiley
& Sons: 2013.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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■
Lett. 1967, 5 (9), 753−759.
(30) Leclerc, M.; Morin, J.-F. Design and Synthesis of Conjugated
Polymers; John Wiley & Sons: 2010.
This work was supported by a National Science Foundation
CAREER grant (CHE-1352431). R.T. was supported by the
National Science Foundation REU program (DMR-1157058).
X.Z. thanks Bob and Beth Gower for a Gower Fellowship and
Southern Illinois University for the SIU Doctoral Fellowship.
V.S.’s work was supported by The University of Virginia.
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Nature 2000, 405 (6790), 1030−1033.
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Chem. Phys. Lett. 2014, 616−617, 137−141.
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