BULLETIN OF THE
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Synthesis of Conjugated Copolymer Containing Spirobifluorene Skeleton
KOREAN CHEMICAL SOCIETY
device performances with Gilch and Horner–Emmons reac-
tion polymers showed lower turn-on voltage (3–4 V),
higher brightness (870 cd/m ), and higher current efficiency
1847. (c) L. Lu, T. Zheng, Q. Wu, A. M. Schneider, D. Zhao,
L. Yu, Chem. Rev. 2015, 115, 12666. (d) J. Kim, S. H. Kim,
J. Y. Shim, T. Kim, J. Lee, I. Kim, J. Y. Kim, H. Suh, Bull.
Kor. Chem. Soc. 2016, 37, 506. (e) N. Sylvianti, T. T. Do,
M. A. Marsya, J. Park, Y.-C. Kang, J. H. Kim, Bull. Kor.
Chem. Soc. 2016, 37, 13.
. (a) V. Podzorov, MRS Bull. 2013, 38, 15. (b) H. Sirringhaus,
Adv. Mater. 2014, 26, 1319. (c) C. Wang, H. Dong, W. Hu,
Y. Liu, D. Zhu, Chem. Rev. 2012, 112, 2208. (d) B. Shaik,
Y. R. Noh, H. J. Choi, S. B. Yoon, M. H. Yun, J. Y. Kim,
S.-G. Lee, Bull. Kor. Chem. Soc. 2015, 36, 1215. (e) Y. H.
Ha, H. J. Koh, S. C. Shin, Y.-H. Kim, Bull. Kor. Chem. Soc.
2015, 36, 2051. (f) J. K. Park, Bull. Kor. Chem. Soc. 2015,
2
(0.16–6.5 cd/A) than those of ADMET reaction polymers
P1–P3. The PLED device performance could be correlated
with the molecular weight of the polymer used in the
device fabrication. The molecular weights of the polymers
synthesized by Gilch and Horner–Emmons methods are
higher (Mw = 222 000 and 78 000, respectively) than
those of the P1–P3 polymers by ADMET. ADMET poly-
mers have lower molecular weights, more chain ends, and
higher chain mobility, which can lead to the formation of
more excimers and aggregates, resulting in lower PLED
2
3
3
6, 1749.
17
. (a) R. H. Friend, R. W. Gymer, A. B. Holmes, J. H.
Burroughes, R. N. Marks, C. Taliani, D. D. C. Bradley, D. A.
Dos Santos, J. L. Brédas, M. Lögdlund, W. R. Salaneck,
Nature 1999, 397, 121. (b) M. A. Baldo, D. F. O’Brien, Y.
You, A. Shoustikov, S. Sibley, M. E. Thompson, S. R.
Forrest, Nature 1998, 395, 151. (c) H. Wu, L. Ying, W.
Yang, Y. Cao, Chem. Soc. Rev. 2009, 38, 3391. (d) B. M.
Kim, Q. P. B. Nguyen, J. G. Fan, M. J. Kim, R. Braveenth,
G. W. Kim, J. H. Kwon, K. Y. Chai, Bull. Kor. Chem. Soc.
2015, 36, 1303. (e) J. E. Song, S. E. Lee, Y. R. Song, T. W.
Kim, C. W. Lim, Y. K. Kim, Bull. Kor. Chem. Soc. 2017,
performance. Therefore, to improve the PLED perfor-
mances of ADMET polymers, more efficient metathesis
catalysts affording ADMET polymers with higher polymer-
ization degrees should be developed.
Conclusion
We have synthesized fluorene-divinylene-based polymers
by ADMET polymerization with Grubbs-type, Hoveyda-
type, CAAC-based ruthenium olefin metathesis catalysts.
Under optimized catalysts and conditions, we cop-
olymerized various ratios of DVF/TVSF by ADMET poly-
merization. The properties of the synthesized copolymers
P1 to P7 and the GPC results indicate that a higher ratio of
TVSF during copolymer polymerization leads to lower sol-
ubility and thus decreases the degree of polymerization.
Investigation by UV–vis spectroscopy showed that an
increase in the TVSF ratio in the copolymer did not change
the electronic properties of the backbone, but showed a nar-
row band in the photoluminescence spectrum. PLED
devices were fabricated with P1, P2, and P3, and the results
indicated that the more spirobifluorene blocks were
included, the better was the performance of the device.
3
8, 1003.
4
. (a) I. Kang, T. K. An, J. A. Hong, H. J. Yun, R. Kim, D. S.
Chung, C. E. Park, Y. H. Kim, S. K. Kwon, Adv. Mater.
2
013, 25, 524. (b) J. Kim, K. J. Baeg, D. Khim, D. T. James,
J. S. Kim, B. Lim, J. M. Yun, H. G. Jeong, P. S. K.
Amegadze, Y. Y. Noh, D. Y. Kim, Chem. Mater. 2013, 25,
1
572. (c) J. Kim, B. Lim, K. J. Baeg, Y. Y. Noh, D. Khim,
H. G. Jeong, J. M. Yun, D. Y. Kim, Chem. Mater. 2011, 23,
4663. (d) J. E. Lee, T. K. An, Y. H. Kim, Macromol. Res.
2016, 24, 629. (e) B. Lim, K. J. Baeg, H. G. Jeong, J. Jo, H.
Kim, J. W. Park, Y. Y. Noh, D. Vak, J. H. Park, J. W. Park,
D. Y. Kim, Adv. Mater. 2009, 21, 2808. (f) B. Lim, J. S.
Yeo, D. Khim, D. Y. Kim, Macromol. Rapid Commun. 2011,
3
2, 1551.
5
6
. (a) S. H. Jin, H. J. Park, J. Y. Kim, K. Lee, S. P. Lee, D. K.
Moon, H. J. Lee, Y. S. Gal, Macromolecules 2002, 35, 7532.
Acknowledgments. This research was supported by the
Technology Development Program to Solve Climate
Changes through the National Research Foundation (NRF)
funded by the Ministry of Science, ICT & Future Planning
(
b) S.-H. Jin, S.-Y. Kang, M. Y. Kim, Y. U. Chan, Macro-
molecules 2003, 36, 3481. (c) D. -H. Hwang, J. -D. Lee,
J.-M. Kang, S. Lee, C.-H. Lee, S.-H. Jin, J. Mater. Chem.
2
003, 13, 1540. (d) W. Meeto, S. Suramitr, S. Vannarat, S.
(NRF-2017M1A2A2049102). This work was also
Hannongbua, Chem. Phys. 2008, 349, 1.
supported by the “Nobel Research Project” grant of the
Grubbs Center for Polymers and Catalysis funded by the
GIST in 2020.
Conflict of Interest. The authors declare no conflict of
interest.
. (a) H. N. Cho, D. Y. Kim, J. K. Kim, C. Y. Kim, Synthet
Metal 1997, 91, 293. (b) R. Grisorio, P. Mastrorilli, C. F.
Nobile, G. Romanazzi, G. P. Suranna, Tetrahedron Lett.
2005, 46, 2555. (c) J. A. Mikroyannidis, Y.-J. Yu, S.-H. Lee,
J.-I. Jin, J. Polym. Sci. Part A: Polym. Chem 2006, 44, 4494.
. (a) P. Anuragudom, S. S. Newaz, S. Phanichphant, T. Randall
Lee, Macromolecules 2006, 39, 3494. (b) P. Auragudom, A.
Tangonan, A. G. Manoj, L. David, R. C. Carroll, S. P.
Advincula, T. R. Lee, J. Polym. Res 2010, 17, 347.
7
8
Supporting Information. Additional supporting informa-
tion may be found online in the Supporting Information
section at the end of the article.
. (a) A. Furstner, Angew. Chem. Int. Ed. 2000, 39, 3012. (b) F.
Boeda, H. Clavier, S. P. Nolan, Chem. Commun. 2008 (24),
2726. (c) S. J. Connon, S. Blechert, Angew. Chem. Int. Ed.
References
2
003, 42, 1900. (d) A. H. Hoveyda, A. R. Zhugralin, Nature
1
. (a) P. Cheng, G. Li, X. Zhan, Y. Yang, Nat. Photonics 2018,
2, 131. (b) R. A. Janssen, J. Nelson, Adv. Mater. 2013, 25,
2007, 450, 243. (e) R. R. Schrock, A. H. Hoveyda, Angew.
Chem. Int. Ed. 2003, 42, 4592.
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