Layer-block dendrimers with alternating thienylenevinylene and phenylenevinylene units

Article abstract of DOI:10.1021/jo301054w

A series of new hybrid, layer-block π-conjugated dendrons and dendrimers with alternating thienylenevinylene and phenylenevinylene units has been prepared by means of an orthogonal and convergent-growth methodology that made use of the Horner-Wadsworth-Emmons (HWE) reaction. The placement of the thiophene and benzene rings can be accurately controlled to afford a large variety of dendritic structures, although access to compounds of high generation proved difficult. The optical properties of the synthesized dendrimers were determined by UV/vis and fluorescence spectroscopy, and the influence of the generation and nature of the core on the behavior of these materials was evaluated.

Full text of DOI:10.1021/jo301054w

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.
julian.rodriguez@uclm.es
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
S
C6H13
C6H13
G0
7.40
7.30
7.20
7.10
7.00
6.90
6.80
6.70
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
S
Solvent: CDCl3
125 MHz
31.5
31.6
S
30.4
S
124.6
C6H13
C6H13
G0
126.7 126.4
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
C
H
13
6
S
C
H
4
6
13
8.00
7.80
7.60
7.40
7.20
7.00
6.80
6.60
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
31.5
COOH
Solvent: CDCl3
125 MHz
S
C6H13
S
4
C6H13
31.6
171.6
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20

S4
CH2OH
Solvent: CDCl3
500 MHz
S
C6H13
S
5
C6H13
7.40
7.30
7.20
7.10
7.00
6.90
6.80
6.70
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
CH2OH
Solvent: CDCl3
125 MHz
S
C6H13
S
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
7.30
7.20
7.10
7.00
6.90
6.80
6.70
6.60
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
CH I
2
Solvent: CDCl
125 MHz
3
S
C H
6
13
S
6
C H
6
13
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
C6H13
S
C6H13
7
Solvent: CDCl
500 MHz
3
7.40
7.30
7.20
7.10
7.00
6.90
6.80
6.70
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
CH2P(O)(OEt)2
S
C6H13
S
7
C6H13
Solvent: CDCl
3
125 MHz
126.6126.4 126.2126.0 125.8125.6 125.4125.2 125.0124.8 124.6124.4 124.2124.0 123.8123.6 123.4123.2 123.0122.8122.6
140
130
120
110
100
90
80
70
60
50
40
30
20

S7
H
O
S
Solvent: CDCl3
500 MHz
S
C6H13
S
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
31.5
C6H13
S
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
S
S
G1
C6H13
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
H
13
6
S
S
C
H
13
6
Solvent: DMSO-d + CDCl
6
3
60 ºC, 125 MHz
S
C
H
13
6
S
S
S
G1
S
C
H
13
6
S
C
H
13
6
S
C
H
13
6
144
142
140
138
136
134
132
130
128
126
124
122
120
140
130
120
110
100
90
80
70
60
50
40
30
20
10

S9
S
Solvent: CDCl3
500 MHz
S
S
G'0
7.50
7.40
7.30
7.20
7.10
7.00
6.90
S
Solvent: CDCl3
125 MHz
S
S
G'0
142
140
138
136
134
132
130
128
126
124
122

S10
C6H13
S
C6H13
S
S
S
S
C6H13
G''1
C6H13
Solvent: CDCl3
500 MHz
7.40
7.30
7.20
7.10
7.00
6.90
6.80
6.70
6.60
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
S
C6H13
S
S
S
S
C6H13
G''1
C6H13
Solvent: CDCl3
125 MHz
128.5 128.0 127.5 127.0 126.5 126.0 125.5 125.0 124.5 124.0 123.5 123.0 122.5 122.0
140
130
120
110
100
90
80
70
60
50
40
30
20

S11
C6H13
S
COOH
S
S
S
S
C6H13
C6H13
10
S
Solvent: DMSO-d6
75 ºC, 500 MHz
C6H13
8.00
7.80
7.60
7.40
7.20
7.00
6.80
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
C6H13
S
COOH
S
S
S
S
C6H13
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
S
CH2OH
S
S
S
S
C6H13
11
C6H13
Solvent: CDCl3
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
S
CH2OH
S
S
S
S
C6H13
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
S
CH2P(O)(OEt)2
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
S
CH2P(O)(OEt)2
S
S
S
S
C6H13
12
C6H13
Solvent: CDCl3
125 MHz
S
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
C6H13
S
C6H13
7.80
7.60
7.40
7.20
7.00
6.80
6.60
6.40
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
1.0
0.8
0.6
0.4
0.2
0.0
G0
G'0
G1
G''1
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).