ability to obtain supramolecular assemblies by forming hydrogen-bonded n-conjugated polymers/oligomers should be a promising approach and would possess unique optical properties (Figure l).4-6
H-N
(2) Abdellatif, M. M.; Nomura, K. ACS Macro Lett. 2012, 1, 423.
(3) Nomura, K.; Yamamoto, N.; Ito, R.; Fujiki, M.; Geerts, Y. Macromolecules 2008, 41, 4245.
(4) Schenning, A. P. H. J.; Jonkheijm, P.; Peeters, E.; Meijer, E. W. J. Am. Chem. Soc. 2001, 123, 409.
(5) Pisula, W.; Tomovic, 2.; Wegner, M.; Graf, R.; Pouderoijen, M. J.; Meijer, E. W.; Schenning, A. P. H. J. J. Mater. Chem. 2008, 18, 2968.
(6) For examples of liquid crystallline diaminotriazine derivates see: (a) Vlad-Bubulak, T.;
Buchs, J.; Kohlmeier, A.; Bruma, M.; Janietz, D. Chem. Mater. 2007, 19, 4460. (b) Maly, K. E.;
Dauphin, C.; Wuest, J. D. J. Mater. Chem. 2006, 16, 4695. (c) Kohlmeier, A.; Janietz, D. Chem.
Mater. 2006, 18, 59.
(1) K. Nomura, and M. M. Abdellatif
"Precise synthesis of polymers containing functional end groups by living ring -opening metathesis polymerization (ROMP): Efficient tools for synthesis of block/graft copolymers"
Polymer, 51, 1861-1881 (2010). Feature article
(2) M. M. Abdellatif, and K. Nomura
"Precise synthesis of amphiphilic multiblock copolymers by combination of acyclic diene metathesis (ADMET) polymerization with atom transfer radical polymerization (ATRP) and click chemistry"
ACS Macro Lett., 1, 423-427 (2012).
(3) M. Fujiki, A. Jalilah, N. Suzuki, M. Taguchi, W. Zhang, M. M. Abdellatif, and K. Nomura
"Chiral optofluidics: gigantic circularly polarized light enhancement of all trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry breaking aggregation by optically tuning fluidic media"
RSC Advances, 2, 6663-6671 (2012).
(4) M. M. Abdellatif, and K. Nomura
"Precise synthesis of oligo(2,5-dialkoxy-1,4-phenylene vinylene)s via combined olefin metathesis and Wittig-type coupling: precise control of repeating units and end functional groups"
Submitted for publication
(5) M. M. Abdellatif, and K. Nomura
"Precise synthesis of well-defined end-functionalized oligo(p-phenylene-1,4-vinylene)s: Effect of conjugation lengths and end-functional groups in optical properties"
Manuscript in preparation.
trans-poly(fluorene-2,7-vinylene) aggregates" (Presented by Prof Fujiki)
International Symposium on Functional Electron Systems (Beijing, China. Oct., 2011).
(2) M. M. Abdellatif, and K. Nomura
"Precise synthesis of amphiphilic block copolymers coupled by metathesis polymerization with atom transfer radical polymerization"
1st CSJ Chemical Festa (Tokyo, Nov., 2011).
(3) M. M. Abdellatif, and K. Nomura
"Precise synthesis of block copolymers utilized by transformation of acyclic diene metathesis (ADMET) to atom transfer radical (ATR) polymerization techniques"
International Symposium on Catalysis and Fine Chemicals (C&FC 2011) (Nara, Dec., 2011).
(4) M. M. Abdellatif, and K. Nomura
"Precise synthesis of block copolymers utilized by transformation of acyclic diene metathesis (ADMET) to atom transfer radical (ATR) polymerization techniques"
Post-symposium of International Symposium on Catalysis and Fine Chemicals (Tokyo, Dec., 2011).
(5) M. M. Abdellatif, and K. Nomura
"Precise synthesis of amphiphilic block copolymers coupled by ADMET with ATR polymerizations"
4th HOPE Meeting (Tsukuba, March, 2012).
(6) M. M. Abdellatif, and K. Nomura
"Precise synthesis of amphiphilic block copolymers coupled by metathesis polymerization with atom transfer radical polymerization, click chemistry"
59th Symposium on Organometallic Chemistry, Japan (Osaka, Sep., 2012) (7) M. M. Abdellatif, and K. Nomura
"Precise synthesis of well-defined end-functionalized oligo-(p-phenylene-1,4-vinylene)s"
12th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12) (Kyoto, Nov., 2012).
Firstly, all praise and glory to Almighty Allah (Subhanahu Wa Taalaa) who gave me courage and patience to carry out this work and completing this thesis.
The author wishes to express his sincere gratitude to Professor Kotohiro NOMURA of the Laboratory of Organic Chemistry, Faculty of Science and Technology, Tokyo Metropolitan University, for his constant guidance, heartwarming encouragement and supervision throughout the course of this research, and for his comments on the presentation of this thesis.
The author is sincerely grateful to Professor Michiya FUJIKI of the Advanced Polymer Science Laboratory, Graduate School of Materials Science, Nara Institute of Science and Technology, for his kindly opportunity to contribute with him in the great research about the unique optical properties of defect free, all-trans poly(fluorene vinylene).
The author is sincerely grateful to Professor Toshio SHIMIZU of the Laboratory of Synthetic Organic Chemistry, Faculty of Science and Technology, Tokyo Metropolitan University, for his valuable constructive suggestions and critical reading for this thesis.
The author is sincerely grateful to Associate Professor NISHINAGA Tohru of Laboratory of Organic Chemistry, Faculty of Science and Technology, Tokyo Metropolitan University, for his valuable discussions and critical reading for this thesis.
The author is sincerely grateful to Associate Professor INAGAKI Akiko of Laboratory of Organic Chemistry, Faculty of Science and Technology, Tokyo Metropolitan University, for his valuable discussions and constructive suggestions for this thesis.
The author is sincerely grateful to Associate Professor SATO Soichi and
Assistant Professor TAKASE Masayoshi of the Faculty of Science and Technology,
Tokyo Metropolitan University, for their valuable discussion and constructive
Abdeltwab of Chemical Industries division, National Research Center of Egypt, for
their warm support, and heartfelt encouragement..
The author would like to expresses his thanks to Ministry of Education, Culture, Sports, Science and Technology (MEXT) for a Japanese government scholarship.
The author would like to thank his colleagues in the Nomura's laboratory in Tokyo Metropolitan University for their encouragement during the course of all research.
Finally, the author really thanks his mother Rawya Gaber, his wife Faten Hassan, his daughter Jana and his brother Soliman Mehawed for their understanding, warm
support, and heartfelt encouragement.
Abdellatif,
January, 2013 Mohamed Mehawed
II ~ I. JL L
PFV-(PS-Br)2
M„=2.99x 104, Mw/M„=1.49
(run 1, Table 1)
PFV-(PS-Br)2
Mn=3.51 x 104, MW/Mn=1.49
(run 2, Table 1)
PFV-(PS-Br)2
M„=6.10x 104, M,„/M„=1.48
(run 3, Table 1)
TS 7s CS Cl 55 51 4.5 4.5 3.5 31 25 21 1.5 to OS ppm
1H NMR spectra for time course of Cu catalyzed ATRP of styrene initiated by PFV(C6H4CH2Br)2
J
PFV-(PS-Br)2
Mn=2.86x 104, MW/M„=1.70
(run 4, Table 1)
J1__
PFV-(PS-Br)2
Mn=3.40x 104, MW/Mn=1.50
(run 5, Table 1)
PFV-(PS-Br)2
Mn=4.10x 104, MW/Mn=1.58
(run 6, Table 1)
7.5 71 45 GA 55 5.4 45 40 55 3.4 23 2A 1.5 1.4 45 ppm
1H NMR spectra for time course of Cu catalyzed ATRP of styrene initiated by PFV(C6H4O0OCMe2Br)2
.i, i l
PFV(C6H4O0OCMe2Br)
ii U
PFV-(PS-Br)2 (run 6, Table 1)
pod minnimel
PI
L —A 1
It -wt. -IrrprIpwwwwww..11/Trwr
PFV-(PS-b/-PEG)2
_ .
No
WIMM
'!J '4 'SJ '434 +•J +JU vJ /J 'U 41 74 •J4J rson
13C NMR spectra for synthesis of PFV -(PS-b/-PEG)2 using PFV(C6H4OCOCMe2Br)2
iampiolopiwoomeLipiWONMow
PFV-(PS-Br)2 (run 3, Table 1)
150 140 130 120 110 100 50 do TO CO 50 40 30 20 0011
1'C NMR spectra for synthesis of PFV -(PS-Br)2 using PFV(C6H4CH2Br)2
22.5 Elution time, min
GPC traces for time course of Cu catalyzed ATRP of styrene initiated by PFV(C6H4CH2Br)2
21 23
Elution time, min
-after 12 hrs - after 24 hrs after 36 hrs
GPC traces for time course of Cu catalyzed ATRP of styrene initiated by PFV(C6H4O0OCMe2Br)2
RO
g f
di
ba
10 9 8 7 6 5 4 3 2 1 ppm
'H NMR spectra of 2
,5-bis(2'-triisopropylsilyloxyethoxy)-1,4-divinylbenzene (up) and its dialdehyde analgous
monomer (down)
RO OPV synthesized using ADMET polymerization
ij
SiMe47.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 10 2.5 2.0 1.5 1.0 0.5 ppm
150 140
1H NMR spectra (up) and
133 120 110 100 90 80 70 60 50 40 30 20 10 pp m
13C NMR (down) of oligo(2
,5-dialkylphenylene-1,4-vinylene)s synthesized by ADMET polymerization technique.
13
OPV-C6F5
OPV-3T
impurity
impurity
1_.I 1.1
o
w A will w.w0.wN
160 140 120 100 BO 60 40 20 0 ppm
C NMR spectra of various end-functionalized oligo(2,5-dialkylphenylene-1,4-vinylene)s
130 -135 -140 -145 .150 -155 -160 -165 ppm
19F NMR spectra of OPV -C6F5
impurity
'Woo 1.1.T.7,11,..,,,TIMITTMIT.W• 1
irrYllfrrIWVFMTWMPTP,P,P0,•••'^1
5PV-C6H5
150 140 130 120 110 100 90 90 70 60 50 40 30 20 ppm
13C NMR spectra of 5PV -3T, 5PV-C6H5 and 5PV- C6F5
-130 -135 -140 -145 -150 -155 -160 -165 ppm
19F NMR spectra of 5PV -C6F5
97