Supporting Information
Time Resolved Structural Dynamics of Butadiyne-Linked
Porphyrin Dimers
Franco V. A. Camargo,1,3 Christopher R. Hall,1 Harry L. Anderson,2 Stephen R. Meech1 and
Ismael A. Heisler1,*
1
School of Chemistry, Norwich Research Park, University of East Anglia, Norwich
NR4 7TJ, United Kingdom
2
Department of Chemistry, University of Oxford, Chemistry Research Laboratory,
Oxford OX1 3TA, United Kingdom
3
CAPES Foundation, Ministry of Education of Brazil, Brasilia - DF 70040-202, Brazil
*Corresponding author. Email: i.heisler@uea.ac.uk, phone: +44 01603 591880.
Table of Contents
Figure S1 Porphyrin monomer and dimer linear absorption and fluorescence spectra
S2
Figure S2 Evolutionary associated spectra
S3
Figure S3 Comparison between measured data and fit for 13513 cm-1 excitation
S4
Figure S4 Comparison between measured data and fit for 15037 cm-1 excitation
S5
Figure S5 Time resolved transient absorption spectra for various excitations
S6
S1
Wavelength(nm)
714
625
556
500
455
417
Wavelength(nm)
385
357
333
313
833
1.8
714
667
625
15
16
588
556
526
17
18
19
556
526
P1 Absorption
P1
1.6
P1 Fluorescence
P2
0.25
P2.L
Amplitude (arb. unit)
1.4
Absorption (arb. unit)
769
0.30
1.2
1.0
0.8
0.6
0.20
0.15
0.10
0.4
0.05
0.2
0.0
0.00
14
16
18
20
22
24
26
28
30
32
12
13
-1
14
-1
Wavenumber (1000 cm )
Wavenumber (1000 cm )
(a)
(b)
Wavelength(nm)
833
769
714
667
625
Wavelength(nm)
588
556
526
833
0.40
769
714
667
625
588
0.40
P2 Absorption
P2 Fluorescence
0.35
P2.L Absorption
0.35
P2.L Fluorescence
0.30
Amplitude (arb. unit)
Amplitude (arb. unit)
0.30
0.25
0.20
0.15
0.25
0.20
0.15
0.10
0.10
0.05
0.05
0.00
0.00
12
13
14
15
16
17
-1
Wavenumber (1000 cm )
(c)
18
19
12
13
14
15
16
17
18
19
-1
Wavenumber (1000 cm )
(d)
Figure S1. (a) UV-Vis linear absorption spectrum of the porphyrin monomer (P1 – green line),
porphyrin dimer (P2 – cyan line) and porphyrin dimer plus ligand (P2•L – magenta line). Molecular
structures are shown in Figure 1(a) in the manuscript. The graphs shown in (b), (c) and (d) are the
fluorescence (red line) and linear absorption (blue line) spectra for the porphyrin monomer (P1),
porphyrin dimer (P2) and porphyrin dimer plus ligand (P2•L), respectively. All the spectra were
recorded in pentane containing 1% pyridine at 298 K. For the Fluorescence spectra, the excitation
was at 20284 cm-1 (493 nm) for P2 and P2•L, whereas for P1 it was at 16129 cm-1 (620 nm).
S2
0
0
-10
-10
 = 1.5 ps
 = 40 ps
 = 232 ps
 = 1.0 ns
-30
-40
EAS (mOD)
EAS (mOD)
-20
-20
 = 1.2 ps
 = 44 ps
 = 1.0 ns
-30
-40
-50
-60
-50
-70
-60
-80
-70
11
12
13
14
15
16
17
18
19
11
20
12
Wavenumber (1000 cm-1)
13
14
15
16
17
18
19
20
Wavenumber (1000 cm-1)
(a)
(b)
20
2
0
-2
0
-20
 = 1.5 ps
 = 34 ps
 = 66 ps
 = 495 ps
 = 1.0 ns
-40
-60
EAS (mOD)
EAS(mOD)
-4
 = 2 ps
 = 50 ps
 = 1.0 ns
-6
-8
-10
-12
-14
-16
-18
-20
-22
-80
11
12
13
14
15
16
17
Wavenumber (1000 cm-1)
(c)
18
19
20
11
12
13
14
15
16
17
18
19
20
Wavenumber (1000 cm-1)
(d)
Figure S2. Evolutionary associated spectra (EAS) resulting from the global analysis fitting procedure
for (a) P2 excited at 13513 cm-1, (b) P2.L excited at 13513 cm-1, (c) P2 excited at 15037 cm-1 and (d)
P2.L excited at 15037 cm-1.
S3
10
B
A
D
C
0
-10
Time (ps)
0.14
1
5
10
20
30
50
100
300
600
A (mOD)
-20
-30
-40
-50
-60
-70
-80
11
12
13
14
15
16
17
18
19
20
Wavenumber (1000 cm-1)
(a)
A  = 12140 cm
pr
-1
B  = 13624 cm-1
pr
P2.L
0.0
P2
-0.5
Fit
P2.L
0
P2
Fit
-1.0
-1.5
-20
-2.5
A (mOD)
A (mOD)
-2.0
-3.0
-3.5
-4.0
-4.5
-40
-60
-5.0
-5.5
-6.0
-80
-6.5
0
100
200
300
400
500
600
0
100
200
Time (ps)
300
400
500
600
Time (ps)
(b)
(c)
C  = 15057 cm-1
pr
P2.L
D  = 16660 cm-1
pr
P2
-0.5
P2.L
5
P2
Fit
Fit
-1.0
4
-2.0
A (mOD)
A (mOD)
-1.5
-2.5
-3.0
3
2
-3.5
-4.0
1
-4.5
-5.0
0
0
100
200
300
Time (ps)
(d)
400
500
600
0
100
200
300
400
500
600
Time (ps)
(e)
Figure S3. (a) Time resolved transient absorption spectra for P2 in pentane (containing 1% pyridine at
298 K) excited at 13513 cm-1 (black arrow) for population times shown in the graph. Labels A to D
point to spectral positions for which specific time traces are compared to equivalent time traces
obtained for P2•L and shown in figures (b) for position A, (c) for position B, (d) for position C and (e)
for position D. The red line in figures (b), (c), (d) and (e) correspond to fits obtained by fitting each
time trace independently.
S4
A  = 12190 cm-1
pr
B
A
20
D
C
P2.L
1
E
P2
Fit
0
10
-1
-2
Time (ps)
0.14
1
5
10
20
30
50
100
300
600
-20
-30
-40
-50
-60
A (mOD)
A (mOD)
0
-10
-3
-4
-5
-6
-7
-70
-8
11
12
13
14
15
16
17
18
19
0
20
100
200
Wavenumber (1000 cm-1)
300
400
500
600
Time (ps)
(a)
(b)
B  = 13663 cm-1
pr
P2.L
P2.L
C  = 15130 cm-1
pr
P2
0
P2
0
Fit
Fit
-5
-10
-10
-15
-20
-25
A (mOD)
A (mOD)
-20
-30
-35
-40
-45
-30
-40
-50
-50
-55
-60
-60
-65
-70
-70
0
100
200
300
400
500
600
0
200
Time (ps)
(c)
600
(d)
D  = 15626 cm-1
pr
E  pr = 18760 cm
P2.L
-1
P2.L
22
P2
12
P2
20
Fit
11
Fit
18
10
16
9
14
8
A (mOD)
A (mOD)
400
Time (ps)
12
10
8
7
6
5
4
6
3
4
2
2
1
0
0
0
100
200
300
Time (ps)
(e)
400
500
600
0
100
200
300
400
500
600
Time (ps)
(f)
Figure S4. (a) Time resolved transient absorption spectra for P2 in pentane (containing 1% pyridine at
298 K) excited at 15037 cm-1 (black arrow) for population times shown in the graph. Labels A to E
point to spectral positions for which specific time traces are compared to equivalent time traces
obtained for P2•L and shown in figures (b) for position A, (c) for position B, (d) for position C, (e) for
position D and (f) for position E. The red line in figures (b), (c), (d), (e) and (f) correspond to fits
obtained by fitting each time trace independently.
S5
30
30
20
20
10
10
0
0
-10
Time (ps)
0.14
1
5
10
20
30
50
100
300
600
-20
-30
-40
-50
-60
-70
-80
A (mOD)
A (mOD)
-10
Time (ps)
0.14
1
5
10
20
30
50
100
300
600
-20
-30
-40
-50
-60
-70
-80
-90
-90
-100
-100
11
12
13
14
15
16
17
18
19
11
20
12
13
Wavenumber (1000 cm-1)
14
(a)
16
17
18
19
20
(b)
30
30
20
20
10
10
0
0
Time (ps)
0.14
1
5
10
20
30
50
100
300
600
-20
-30
-40
-50
-60
-70
-80
Time (ps)
0.14
1
5
10
20
30
50
100
300
600
-10
A (mOD)
-10
A (mOD)
15
Wavenumber (1000 cm-1)
-20
-30
-40
-50
-60
-70
-80
-90
-90
-100
-100
11
12
13
14
15
16
17
18
19
20
11
12
13
Wavenumber (1000 cm-1)
14
15
16
17
18
19
20
Wavenumber (1000 cm-1)
(c)
(d)
30
20
10
0
A (mOD)
-10
Time (ps)
0.14
1
5
10
20
30
50
100
300
600
-20
-30
-40
-50
-60
-70
-80
-90
-100
11
12
13
14
15
16
17
18
19
20
Wavenumber (1000 cm-1)
(e)
Figure S5. Time resolved transient absorption spectra for P2 in pentane (containing 1% pyridine at
298 K) excited at different wavenumbers as shown by the black arrows. The population times are
shown in the graph.
S6