Additional Supporting Information
Anionic Alternating Copolymerization of α-Arylacrylates with Methyl Methacrylate:
Effect of Monomer Sequence on Fluorescence
Yasuhiro Kohsaka, Eiji Yamaguchi, Tatsuki Kitayama
Department of Chemistry, Graduate School of Engineering Science, Osaka University, 1-2 Machikaneyama,
Toyonaka, Osaka 560-8531, Japan
Correspondence to: Tatsuki Kitayama (E-mail: kitayama@chem.es.osaka-u.ac.jp)
1. Scheme of monomer synthesis.
2. Polymerization of α-arylacrylates.
3. Optical properties of Np2 polymers
4. Spectral charts.
1. Scheme of monomer synthesis.
Scheme S1. Synthesis of Py1.
Scheme S2. Synthesis of Np1.
Scheme S3. Synthesis of Np2.
Scheme S4. Synthesis of Fl2.
2. Polymerization of α-arylacrylates.
Table S1. Anionic (co)polymerization of Py1 with MMA initiated by Li-iPrIB in toluene.a
Run
[MMA]0 /[Py1]0
Temp. /°C
S1
0
0
S2
0
30
1.0
30
S3
a)
Time /h
Yield /%
0
96
0
48
0
EPyA = 2.0 mmol, ([EFA]0 + [MMA]0)/[Li-iPrIB]0 = 20 /1, toluene = 2.0 mL.
(a)
(b)
Figure 3-2. Reaction mixture of (a) homopolymerization of EPyA, and (b) copolyPy1
with MMA.
merization
of EPyA and MMA.
Figure S1. Photograph of the reaction mixture in homopolymerization (RunS1) and copolymerization (Run S3) of
Table S2. Group transfer (co)polymerization of Py1 with MMA.a
[MMA]0 /[Py1]0
[Bu4N+F-]0 / [MTS]0
Yield /%
S4a
0
0.10
0
a
0
0.0010
0
0
0.10
Not described
1.0
0.10
0
Run
S5
Refb
S6
a) EPyA = 2.0 mmol, [EFA]0 /[MTS]0 = 20 /1,THF = 1.0 mL, rt, 8 h.
b) Reported in the following article: M. A. Fox, H. W. Thompson, Macromolecules, 1997,
30, 7391-7396.
(a)
(b)
Figure S2. Photograph of the reaction mixture in homopolymerization (RunS4) and copolymerization (Run S6) of
Py1 with MMA.
3. Optical properties of Np2 polymers
FIGURE S3 Absorption spectra of (A) oligo(Npl2), and (B) poly(Np2-co-MMA) (in CHCl3, [naphthalene moiety]0 =
2.0  10–4 M).
FIGURE S4 Emission spectra of (A) oligo(Np2) and (B) poly(Np2-co-MMA) (in CHCl3, [naphthalene moiety]0 = 2.0 
10–4 M, λex = 270 nm).
4. Spectral charts.
1
H NMR spectrum of 1 (400 MHz, CDCl3, 30 °C).
1
H NMR spectrum of 2 (400 MHz, CDCl3, 30 °C).
1
H NMR spectrum of Py1 (400 MHz, CDCl3, 30 °C).
13
C NMR (bottom) and DEPT 135 (top) spectra of Py1 (100 MHz, CDCl3, 30 °C).
1
H NMR spectrum of Np1 (400 MHz, CDCl3, 30 °C).
13
C NMR (bottom) and DEPT 135 (top) spectra of Np1 (100 MHz, CDCl3, 30 °C).
1
H NMR spectrum of 3 (400 MHz, CDCl3, 30 °C).
1
H NMR spectrum of 4 (500 MHz, CDCl3, 30 °C).
1
H NMR spectrum of Np2 (400 MHz, CDCl3, 30 °C).
13
C NMR (bottom) and DEPT 135 (top) spectra of Np2 (100 MHz, CDCl3, 30 °C).
1
H NMR spectrum of 5 (400 MHz, CDCl3, 30 °C).
1
H NMR spectrum of 6 (400 MHz, CDCl3, 30 °C).
1
H NMR spectrum of Fl2 (400 MHz, CDCl3, 30 °C).
13
C NMR (bottom) and DEPT 135 (top) spectra of Fl2 (100 MHz, CDCl3, 30 °C).