Upload
argyle
View
19
Download
0
Tags:
Embed Size (px)
DESCRIPTION
Analytical and structural evaluation of poly(3-hexylthiophene)s formed by chemical oxidative coupling methods: the role of experimental conditions in their design. Warren Solfiell McCarley Research Group Department of Chemistry Louisiana State University Baton Rouge November 16 2009. - PowerPoint PPT Presentation
Citation preview
Analytical and structural evaluation of poly(3-hexylthiophene)s formed by chemical oxidative
coupling methods: the role of experimental conditions in their design
Warren SolfiellMcCarley Research GroupDepartment of ChemistryLouisiana State University
Baton RougeNovember 16 2009
1
Pyrrole Monomer capped dendrimer
Oxidative coupling
Reducing agent
Oligomerized monomer units
DAB-(Py)32
2
Capture and release dendrimers
N
N
N
N
N
N
N
N
N
N
N
N
link to dendrimer
N
N
N
N
R
R
R
R
N
N
N
N
R
R
R
X-
R
n
n
Reduction
N
N
N
R
R
R
OxidativeOligomerizaton
N
R
polaron
N
N
N
N
R
R
R
X-
R
n
bipolaron
X-
FurtherOxidation
neutral polymer
oxidized
reduced
3
Oxidation of poly(pyrrole)s for capture and release
S
oligo(3-alkylthiophene)
nS S
S
H
H
R
R
R
R
N
R
N
R
N
R
N
R
N
R
N
R
N
R
N
R
N
R
N
R
H
H
oligo(N-alkylpyrrole)
n
Heterocyclic Conducting Polymers
4
•Field Effect Transistors•Oganic/biological sensors•OLEDs•Flexible Displays•Solar Cells•Antistatic•Printable conductive ink•Anti-corrosion•RFID tags
5
1.00 mmol of FeCl3 in 12.5 mL solvent used (80 mM)
stir 1 hour (@RT) under argon
1.00 mmol of monomerin 12.5 mL solvent used (80 mM)
quench with MeOH
24 hours
then washed and extractedwith 300 mL 2.0N HCl
and 200 mL chloroform
solid polymer is filtered off
chloroform is rotary-evaporatedand polymer film
is dried under highvacuum to constant mass
6
Polymerization procedure for chemical oxidative coupling
S S H
SH
SSH H Soxidation
dimer
S
S H
H
+ + ++
+
-2H+ oxidationR FeCl3 RR
R
R R
S
R
R
R
S
S
+
R
RH
S
S
SE1 E2
R R
R
n
C. head-to-tail-head-to-head
S
S
SE1 E2
R R
R
n
D. tail-to-tail-head-to-head
S E2
R
n
S
S
R
R
E1
A. head-to-tail-head-to-tail
S
S
S E2E1
R R
Rn
B. tail-to-tail-head-to-tail
oligomerization
7
Oxidation pathway for heterocyclic conducting polymers
OVERVIEWS E2
R
n
SS
R
R
E1
A. head-to-tail-head-to-tail
SS
S E2E1
R R
Rn
B. tail-to-tail-head-to-tail
SS
SE1 E2
R R
Rn
C. head-to-tail-head-to-head
S
S
SE1 E2
R R
Rn
D. tail-to-tail-head-to-head8
Figured adapted from; www.psrc.usm.edu/ mauritz/images/maldi2b.jpg
Matrix-assisted laser desorption and ionization (MALDI)
9
Figure adapted from; Dass, C. Principles and Practice of Biological Mass Spectrometry; Wiley-Interscience: New York, 2001.
2
1
2
zV
mL
v
Lt
MALDI- Time of flight (Tof) Mass spectrometry
10
Mend = Mpeak - Mcat - nMrep
Mend = Mpeak - Mprot - nMrep
Mend = Mpeak - Melec - nMrep
[M].+
MALDI- Time of flight (Tof) Mass spectrometry
11
and http://www.sci.sdsu.edu/TFrey/Bio750/Chroma4.gif
figures adapted from; http://content.answers.com/main/content/img/McGrawHill/Encyclopedia/images/CE283900FG0010.gif
Size exclusion chromatography (SEC)
12
Part One: Modifications to polymerization procedures for chemical oxidative coupling of poly(3-hexylthiophene)s
13
S
SS
TerthiopheneMW 248.4
CH3
CN
CNH3C
H3CCH3
trans-2-[3-(4-tert-Butylphenyl)-2-methyl-2-propenylidene]malononitrile
MW 250.34
"DCTB"
Matrix assisted laser desorption and ionization (MALDI) matrices
14
750 1000 1250 1500 1750 2000 2250 2500 2750 3000 3250 35000
2000
4000
6000
8000
10000
Abundance
m/z
0 1300 2600 3900 52000.00
7.50x102
1.50x103
2.25x103
3.00x103
n =
30
n =
29
n =
28
n =
27
n =
26
n =
25
n =
24
n =
23
n =
22
n =
21
n =
20
n =
19
n =
18
n =
17
n =
16
n =
15
n =
14
n =
10
n =
9
n =
8
n =
13
n =
12
n =
11
¾n
= 7
n =
6
n =
5
Rela
tive A
bundance
m/z
MALDI spectra P3HT made in chloroform -Top spectra terthiophene matrix -Bottom spectra DCTB matrix
15
MALDI spectrum P3HT made in nitromethanewith 1:2.5 monomer:oxidant ratio
terthiophene matrix
16
0 1600 3200 4800 64000.0
5.0x102
1.0x103
1.5x103
2.0x103
n =
10
n =
9
n =
36
n =
35
n =
34
n =
33
n =
32
n =
31
n =
30
n =
29
n =
28
n =
27
n =
26
n =
25
n =
24
n =
23
n =
22
n =
21
n =
20
n =
19
n =
18
n =
17
n =
16
n =
15
n =
14
n =
13
n =
11
n =
8
n =
12
n =
7
n =
6
IS
IS
Rela
tive A
bundance
m/z
IS
1000 1025 1050 10750.00
6.30x102
1.26x103
1.89x103
Rel
ativ
e A
bund
ance
m/z
n = 6 [M]·
E1= H, E
2= H
E1= H, E
2= O
E1= H, E
2= Cl
E1= Cl, E
2= Cl
1150 1175 1200 1225 12500.00
3.30x102
6.60x102
9.90x102R
elat
ive
Ab
un
dan
ce
m/z
n = 7 [M]·
E1= H, E
2= H
E1= H, E
2= O
E1= H, E
2= Cl
E1= Cl, E
2= Cl
MALDI spectra solid P3HT made in nitromethane DCTB matrix
spectrum
17
0 1500 3000 4500 60000
2500
5000
7500
10000R
ela
tive A
bundance
m/z
825 850 875 9000
100
200
300
400
Observed H, H calculated H, O calculated H, Cl calculated
Rel
ativ
e A
bund
ance
m/z
End-group analysisn = 5
[M]·+
1150 1175 1200 1225 12500
250
500
750
1000
Observed H, H calculated H, O calculated H, Cl calculated
Rel
ativ
e A
bund
ance
m/z
End-group analysisn = 7
[M]·+
MALDI spectra soluble P3HT made in nitromethane DCTB matrix
spectrum
18
1H-NMR P3HT made in nitromethane
-soluble fraction above-Solid precipitate below
67%
26%
19
Conclusions-Part One
• DCTB, a previously unreported matrix for use with poly(alkylthiophene)s, is preferable and beneficial for MALDI analysis of these materials
• Soluble material from the chemical oxidative coupling polymerization of these materials is not useful product
• Decreasing the monomer to oxidant ratio for these polymerizations does reduce the chlorine addition to these materials but does not produce only hydrogen
terminated product
• Ion discrimination does occur during MALDI ionization between chlorinated and non-chlorinated oligomers which is dependent on the extent of halogenation
• Sample preparation and choice of matrices is crucial
20
Part Two: Characterization of effects to the physicalproperties of poly(3-hexylthiophene)s
made by chemical oxidation at low-temperatures
21
0 1600 3200 4800 64000.0
5.0x102
1.0x103
1.5x103
2.0x103
n =
10
n =
9
n =
36
n =
35
n =
34
n =
33
n =
32
n =
31
n =
30
n =
29
n =
28
n =
27
n =
26
n =
25
n =
24
n =
23
n =
22
n =
21
n =
20
n =
19
n =
18
n =
17
n =
16
n =
15
n =
14
n =
13
n =
11
n =
8
n =
12
n =
7
n =
6
IS
IS
Rela
tive A
bundance
m/z
IS
1000 1025 1050 10750.00
6.30x102
1.26x103
1.89x103
Rel
ativ
e A
bund
ance
m/z
n = 6 [M]·
E1= H, E
2= H
E1= H, E
2= O
E1= H, E
2= Cl
E1= Cl, E
2= Cl
1150 1175 1200 1225 12500.00
3.30x102
6.60x102
9.90x102R
elat
ive
Ab
un
dan
ce
m/z
n = 7 [M]·
E1= H, E
2= H
E1= H, E
2= O
E1= H, E
2= Cl
E1= Cl, E
2= Cl
MALDI spectra solid P3HT made in nitromethane @ room temperature DCTB matrix
spectrum
22
0 1600 3200 4800 6400
7.50x102
1.50x103
2.25x103
3.00x103
n =
3
n =
36
n =
35
n =
34
n =
33
n =
32
n =
31
n =
30
n =
29
n =
28
¾ n
= 2
7
n =
26
n =
25
n =
24
n =
23
n =
22
n =
21
n =
20
n =
19
n =
18
n =
17
n =
16 n =
15
n =
14
n =
13
n =
12
n =
11
n =
10
n =
9
n =
8 n =
7
n =
6
IS
IS
n =
5
IS
Rela
tive A
bundance
m/z
1000 1025 1050 10750.00
6.30x102
1.26x103
1.89x103
Rel
ativ
e A
bund
ance
m/z
[M]·n = 6
E1= H, E
2= H
E1= H, E
2= O
E1= H, E
2= Cl
E1= Cl, E
2= Cl
1150 1175 1200 1225 12500.00
4.40x102
8.80x102
1.32x103
E1= H, E
2= H
E1= H, E
2= O
E1= H, E
2= Cl
E1= Cl, E
2= Cl
Rel
ativ
e A
bund
ance
m/z
[M]·n = 7
MALDI spectra solid P3HT made in nitromethane @ - 30 ºC DCTB matrix
spectrum
23
0 1300 2600 3900 52000.00
7.50x102
1.50x103
2.25x103
3.00x103
n =
30
n =
29
n =
28
n =
27
n =
26
n =
25
n =
24
n =
23
n =
22
n =
21
n =
20
n =
19
n =
18
n =
17
n =
16
n =
15
n =
14
n =
10
n =
9
n =
8
n =
13
n =
12
n =
11
¾n
= 7
n =
6
n =
5
Rela
tive A
bundance
m/z
1000 1025 1050 10750.00
2.50x102
5.00x102
7.50x102
1.00x103
E1= H, E
2= H
E1= H, E
2= Cl
E1= Cl, E
2= Cl
Rel
ativ
e A
bund
ance
m/z
[M]·n = 6
825 850 875 9000.00
4.40x102
8.80x102
1.32x103
[M]·n = 5
E1= H, E
2= H
E1= H, E
2= Cl
E1= Cl, E
2= Cl
Rel
ativ
e A
bund
ance
m/z
MALDI spectra solid P3HT made in chloroform @ room temperature DCTB matrix
spectrum
24
1000 1025 1050 10750.00
3.80x102
7.60x102
1.14x103
Rel
ativ
e A
bund
ance
m/z
E1= H, E
2= H
E1= H, E
2= Cl
E1= Cl, E
2= Cl
[M]·n = 6
1150 1175 1200 1225 12500.00
3.80x102
7.60x102
1.14x103
Rel
ativ
e A
bund
ance
m/z
[M]·n = 7
E1= H, E
2= H
E1= H, E
2= Cl
E1= Cl, E
2= Cl
0 1300 2600 3900 52000.00
7.50x102
1.50x103
2.25x103
3.00x103
n =
30
n =
29
n =
28
n =
27
n =
26
n =
25
n =
24
n =
23
n =
22
n =
21
n =
20
n =
19
n =
18
n =
17
n =
16
n =
15
n =
14
n =
13
n =
12
n =
11
n =
10
n =
9 n =
8 n =
7
n =
6
n =
5
Relative A
bundance
m/z
MALDI spectra solid P3HT made in chloroform @ - 30 ºC DCTB matrix
spectrum
25
A B
C D78%
77%
51%
65%
Chloroform Nitromethane
26
1H-NMR comparisons of room temperature and low-temperature polymerizations
Conclusions-Part Two
• Shift in equilibrium between active species (Fe2Cl5+ /FeCl2
+ ) could
be attributed to reduced chlorination as the result of several factors• FeCl3 becomes more soluble during these low-temperature polymerizations
• Dielectric constant slightly increases
• Reaction time increases (from 1 to 24 hours)
• Low temperature slows kinetics of reaction
• Regio-regularity only slightly improves for certain solvents•Still a random event
•Radical lifetimes are dependent on solvent and prolonged with reduced temperature
•Oxidation potentials are reduced as oligomer chain grows and oligomer-oligomer coupling may be preferable for certain solvents regardless of temperature
Equation 1 2FeCl3 FeCl2+ + FeCl4¯
Equation 2 2FeCl3 Fe2Cl5+ + Cl¯
27
Part Three: Characterization of solvent effects on polymerization and physical properties of
poly(3-hexylthiophene)s made by chemical oxidation
28
Solventpermittivity
(ϵ)@20 ◦C
donor number (DN)
kcal/mol
acceptor number (AN)
chloroform 4.8 negligible 23nitromethane 37 2.7 20.5
carbon tetrachloride 2.2 9 8.61,2-dichloroethane 10.4 negligible 100* SbCl5 in DCE
acetonitrile 36.6 14.1 19.3toluene 2.4 0.1 8.2* benzene
nitrobenzene 35.7 4.4 14.8hexane 1.9 0*benzene 2.3 0.01 8.2
dichloromethane 9.1 Benzonitrile 26 11.9 15.5nitropropane 17 diethyl ether 4.3 19.2 3.9
triethyl amine 2.4 61* neglibleacetone 21 17 12.5
Bromoform 4.4
Solvents employed for solvent effect studies
29
0 1300 2600 39000.00
1.50x103
3.00x103
4.50x103
6.00x103R
elative A
bundance
m/z
Solid poly(3-hexylthiophene) formed in 1, 2-dichloroethane with iron III chlorideat RT for 1 hr using 1:1 mon:oxidant ratio; DCTB matrix
81% regio-regular
MALDI spectra solid P3HT made in 1, 2-dichloroethane @ room temperature; DCTB matrix
1,2 -dichloroethane
ɛ r = 10.4An = 100 *Dn = negligibleYield = 25% (45 mg)
spectrum
30
1H-NMR of P3HT made in 1,2-dichloroethane at room temperature
0 1300 2600 39000.0
5.0x102
1.0x103
1.5x103
2.0x103R
elative A
bundance
m/z
Solid poly(3-hexylthiophene) formed in acetonitrile with iron III chlorideat RT for 1 hr using 1:1 mon:oxidant ratio; DCTB matrix
75% regio-regular
MALDI spectra solid P3HT made in acetonitrile @ room temperature; DCTB matrix
acetonitrile
ɛ r = 36.6An =19.3Dn =14.1Yield = 27% (46 mg)
spectrum
31
1H-NMR of P3HT made in acetonitrile at room temperature
0 1400 2800 42000
750
1500
2250
3000R
elative A
bundance
m/z
poly(3-hexylthiophene) formed with ferric chloride in nitrobenzeneat room temp for 1 hour using 1:1 mon:ox ratio
67% regio-regular
MALDI spectra solid P3HT made in nitrobenzene @ room temperature; DCTB matrix
nitrobenzene
ɛ r = 35.7An = 14.8Dn = 4.4Yield = 13% (21 mg)
spectrum
32
1H-NMR of P3HT made in nitrobenzeneat room temperature
Comparison of number average (Mn) molecular weights from SEC
33
Comparison of polydispersities from SEC
34
Conclusions-Part Three
• Solvents with strong Lewis basicity (large Donor number) complex the active species of oxidant disabling active species interaction with monomer
• Degree of polymerization may depend more on active species interaction with solvent than monomer
• Large dielectric constants (i.e. solubility) is not the only reason for presence of tetrachloroferrate ion (as is the case with acetonitrile)
• Appears as though solvents with large dielectric constants and with strong Lewis acidity (large Acceptor number) shift equilibrium to tetrachloroferrate population
• Solvent plays a large role in lifetimes of ionic species i.e monomer, dimer , trimer etc. influencing polymer growth and therefore regioregularity
• Solvent also influences coupling rates reflected in regioregularity
Equation 1 2FeCl3 FeCl2+ + FeCl4¯
Equation 2 2FeCl3 Fe2Cl5+ + Cl¯
35
Part Four: Semi-preparative size exclusion chromatography for the fractionation of
poly(3-hexylthiophene)s made by chemical oxidation
36
10.4 11.7 13.0 14.3 15.6 16.9 18.2 19.5 20.8 22.1 23.40.1
0.2
0.3
0.4
0.5
0.6
0.7
12111098765432
SEC on semi-prep column of 7.6 mg/mL solid p3ht formed in tolueneat RT with iron(I I I) chloride for 1 hour using 1:1 mon:ox ratio1 mL injection 10 mL/min flow rate; 12 collection @ 1 min/ea
Inte
nsit
y
Ve (mL)
1
37
Fraction 3 - 77%
Fraction 1 - 77% 1H-NMR spectra of toluene fractions collected from semi-prep GPC
38
Fraction 6 - 68%
Fraction 4 - 77%
1H-NMR spectra of toluene fractions collected from semi-prep GPC
39
Fraction 8 - 55%
Fraction 7 - 62% 1H-NMR spectra of toluene fractions collected from semi-prep GPC
40
300 450 600 7500.00
0.63
1.26
1.89
D042_1 D042_2 D042_3 D042_4 D042_5 D042_6 D042_7 D042_8A
U
Wavelength (nm)
D042_all Toluene RT 1 to 1 1 hour solidUV-Vis spectrum of toluene fractions from semi-prep GPC
41
Conclusions-Part Four• Appears to be different structures or states of polymer as represented
by interactions of analyte with gel permeation column
• Semi-preparative fractionation seems to be able to effectively separate analyte for molecular weight and structural studies with some modification to procedure
• Evidence of change in regularity for different molecular weights which makes sense as larger polymer should be more regular material
• Procedure may enable obtaining more desirable product made through chemical oxidative coupling polymerization
42
Future Work
• Experiments to further confirm shifts of active species dependent on solvent and temperature
• Examine fractions obtained from semi-preparative GPC with MALDI for clarification of species or reasons for different interactions with GPC column
• Use fractions from semi-preparative GPC in order to further separate individual oligomers, greater than n = 14, in large enough quantities to investigate thoroughly using HPLC
43
Acknowledgements• Prof. Robin L. McCarley• McCarley Research Group• Dr. Rebecca Brauch• Dr. Rafael Cueto• Dr. Evgueni Nesterov• Dr. Azeem Hasan• Dr. Dan Pu• Dr. Kermit Murray • Louisiana State Economic Development Asst.
44