S1
Supporting Information
Layer-Block Dendrimers with Alternating Thienylenevinylene and Phenylenevinylene Units Caroline Hadad,† Joaquín C. García-Martínez,‡ and Julián Rodríguez-López*,† †
Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La Mancha, 13071 Ciudad
Real, Spain. ‡ Facultad de Farmacia, Universidad de Castilla-La Mancha, 02071 Albacete, Spain.
[email protected] Table of contents 1. 1H and 13C NMR spectra for all dendrons and dendrimers (pages S2 to S14). 2. Fluorescence decay profiles for G0, G’0, G’’1 and G1 (page S14).
S2 C6H13 S
Solvent: CDCl3 500 MHz
S C6H13
7.40
7.5
7.0
6.5
7.30
7.20
6.0
5.5
7.10
7.00
6.90
5.0
6.80
4.5
S
C6H13
G0
6.70
4.0
3.5
3.0
2.5
2.0
1.5
1.0
C6H13 S
Solvent: CDCl3 125 MHz
S
124.6
C6H13
126.7 126.4
S G0
31.5 31.6
30.4
C6H13
122.7 122.9
28.8 22.6 14.1
140.4137.9 145.7
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
S3
COOH
Solvent: CDCl3 500 MHz S S C6H13
8.00
8.5
8.0
7.5
7.0
7.80
6.5
7.60
6.0
7.40
5.5
7.20
5.0
7.00
6.80
4.5
C6H13
4
6.60
4.0
3.5
3.0
2.5
2.0
1.5
1.0
31.5
COOH
Solvent: CDCl3 125 MHz S S
C6H13
4
C6H13
31.6
171.6
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
0.5
S4 CH2OH
Solvent: CDCl3 500 MHz S S C6H13
7.40
7.5
7.30
7.0
7.20
6.5
7.10
6.0
7.00
5.5
5.0
6.90
6.80
6.70
4.5
4.0
3.5
C6H13
5
3.0
2.5
2.0
1.5
1.0
CH2OH
Solvent: CDCl3 125 MHz S S
C6H13
5
C6H13
65.3
140
130
120
110
100
90
80
70
60
50
40
30
20
10
S5 CH2I Solvent: CDCl3 500 MHz S
C6H13
S 6
C6H13
7.40
7.5
7.30
7.20
7.0
7.10
6.5
7.00
6.90
6.0
6.80
5.5
6.70
5.0
6.60
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
CH2I Solvent: CDCl3 125 MHz S
C6H13
S 6
C6H13
31.5 31.6
5.41
140
130
120
110
100
90
80
70
60
50
40
30
20
10
S6 CH2P(O)(OEt)2
S S C6H13
C6H13
7 Solvent: CDCl3 500 MHz
7.40
7.30
7.5
7.20
7.0
7.10
6.5
7.00
6.0
6.90
5.5
6.80
6.70
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
CH2P(O)(OEt)2
S S
C6H13
7
C6H13
Solvent: CDCl3 125 MHz
126.6 126.4 126.2 126.0 125.8 125.6 125.4 125.2 125.0 124.8 124.6 124.4 124.2 124.0 123.8 123.6 123.4 123.2 123.0 122.8 122.6
140
130
120
110
100
90
80
70
60
50
40
30
20
S7 H O S
Solvent: CDCl3 500 MHz
S S
C6H13
9
C6H13
7.60
7.40
7.20
7.00
6.80
6.60
9.86
10.0
9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
H O S
Solvent: CDCl3 125 MHz
S S
31.5
C6H13
9
31.6
C6H13
182.6
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
S8 C6H13 S
S
C6H13
Solvent: DMSO-d6 + CDCl3 500 MHz
S
C6H13 S S
C6H13
S
S
G1 S C6H13
S C6H13
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
C 6H13 S
C6H13
S Solvent: DMSO-d 6 + CDCl 3 60 ºC, 125 MHz S C 6H 13 S S
C6 H13
S
G1
S
S C 6H 13
S C6H13
144
140
142
140
130
138
136
120
134
132
110
130
128
100
126
124
122
90
120
80
70
60
50
40
30
20
10
S9 S
Solvent: CDCl3 500 MHz
S
7.50
7.40
S
G'0
7.30
7.20
7.10
7.00
6.90
S
Solvent: CDCl3 125 MHz
S
142
140
138
136
G'0
134
S
132
130
128
126
124
122
S10 C6H13
C6H13 S
S
S S S C6H13
7.40
7.5
7.0
7.30
6.5
7.20
7.10
6.0
7.00
5.5
5.0
6.90
4.5
C6H13
G''1 Solvent: CDCl3 500 MHz
6.80
6.70
4.0
6.60
3.5
3.0
2.5
2.0
1.5
1.0
C6H13
C6H13 S
S
S S S C6H13
128.5
128.0
140
127.5
127.0
130
126.5
126.0
120
125.5
125.0
110
124.5
124.0
100
123.5
123.0
122.5
90
C6H13
G''1 Solvent: CDCl3 125 MHz
122.0
80
70
60
50
40
30
20
0.5
S11 C6H13
COOH
S
S S
S
S
C6H13
C6H13 10 S
Solvent: DMSO-d6 75 ºC, 500 MHz
C6H13
8.00
8.0
7.80
7.5
7.60
7.0
6.5
7.40
7.20
6.0
5.5
7.00
5.0
6.80
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
C6H13
COOH
S
S S
C6H13
S
S 10
C6H13
Solvent: DMSO-d6 75 ºC, 125 MHz
S C6H13
144
142
140
138
136
134
132
130
128
126
124
122
166.7
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
S12 C6H13
CH2OH
S
S S
C6H13
S
S 11
C6H13
Solvent: CDCl 3 500 MHz
S C6H13
7.50
7.40
7.30
7.20
7.10
7.00
6.90
6.80
6.70
6.60
4.72
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
C6H13
CH2OH
S
S S
C6H13
S
S 11
C6H13
Solvent: CDCl3 125 MHz
S C6H13
146
144
142
140
138
136
134
132
130
128
126
124
122
65.2
140
130
120
110
100
90
80
70
60
50
40
30
20
S13 C6H13
CH2P(O)(OEt)2
S
S S
S
S
C6H13
12
C6H13
Solvent: CD3OD + CDCl3 500 MHz
S C6H13
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
C6H13
CH2P(O)(OEt)2
S
S S
C6H13
S
S 12 Solvent: CDCl3 125 MHz
S
C6H13
C6H13
148
146
144
142
140
138
136
134
132
130
128
126
124
122
120
118
62.3
140
130
120
110
100
90
80
70
60
50
40
30
20
10
S14 9.86
CHO S C6H13 S S
S
S
C6H13
13
S
Solvent: CDCl3 500 MHz
S
C6H13
C6H13
7.80
9.5
9.0
8.5
8.0
7.5
7.0
7.60
6.5
7.40
6.0
7.20
5.5
7.00
5.0
6.80
6.60
4.5
4.0
6.40
3.5
3.0
2.5
2.0
1.5
1.0
0.5
INTENSITY NORMALIZED
1.0
G0 G'0 G1 G''1
0.8
0.6
0.4
0.2
0.0 150
160
170
180
190
200
TIME (ns)
FIGURE S1. Fluorescence decay profiles for G0 (black), G’0 (red), G’’1 (green) and G1 (blue) in CH2Cl2 (c = 5.0 x 10-6 M).
