of 17
S
1
Supporting Information
Processing Effects on the Self
-
Assembly of Brush
Block Polymer Photonic Crystals
Allegra L. Liberman
-
Martin,
§
*
Alice B. Chang,
§
Crystal K. Chu,
Radwanul H. Siddique,
Byeongdu Lee,
#
*
and Robert H. Grubbs
*
Schmid College of Science and Technology, Chapman University, Orange, California 92866, United States
† Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125,
United States
‡ Department of
Medical Engineering, California Institute of Technology, Pasadena, California 91125, United States
#
X
-
Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United
States
Email
address
for Allegra L. Liberman
-
Martin:
libermanmartin@chapman.edu
Email
address
for Byeongdu Lee:
blee@anl.gov
Email
address
for Robert H. Grubbs:
rhg@caltech.edu
Table of Contents:
General Considerations
S2
Instrumentation
S2
Synthesis of PDMS and PTMC macromonomers
S3
Homopolymerization of PDMS and PTMC macromonomers
S4
Synthesis of PDMS
b
PTMC Brush Block Polymers
S4
S5
NMR Spectra
S
5
S7
SEC Traces
S7
S
9
Reflectance Spectral Data
S
10
SEM Images
S
10
Photographs of P
DMS
b
PTMC Samples
S1
1
S1
2
SAXS Sample Preparation and Data Collection
S1
3
SAXS Data
S
14
S16
Method to Determine Pressure Applied by Medium Binder Clips
S16
References
S17
S
2
General Considerations
Unless otherwise noted, all manipulations were carried out under an inert atmosphere using
an argon
-
filled glovebox or standard Schlenk techniques. All glassware was oven dried prior to
use.
Solvents were purified by passage
through solvent purification columns
,
1
degassed with
argon, and stored over activated 3 Å molecular sieves.
N
-
(3
-
d
imethylaminopropyl)
-
N
-
ethylcarbodiimide hydrochloride (EDC
·
HCl) and 4
-
d
imethylaminopyridine (DMAP) were purchased from Sigma
-
Aldrich and
used as received. 1,8
-
d
iazabicyclo[5.4.0]undec
-
7
-
ene (DBU) was purchased from Sigma
-
Aldrich, degassed, and stored
over activated 3Å molecular sieves. Monocarbinol
-
terminated polydimethylsiloxane (
M
n
= 1000)
was purchased from Gelest (
MCR
-
C12
). Trimethylene
carbonate was purchased from
Polysciences. (H
2
IMes)(PCy
3
)(Cl)
2
Ru
CHPh was received as a research gift from Materia and
converted to (H
2
IMes)(py)
2
(Cl)
2
Ru
CHPh (
G3
)
via
a literature procedure
.
2
Norbornene
derivatives
N
-
(hexanoic acid)
-
cis
-
5
-
norbornene
-
exo
-
dicarboximide
3
and
N
-
(hydroxyethyl)
-
cis
-
5
-
norbornene
-
exo
-
2,3
-
dicarboximid
e
4
were prepared according to literature procedures.
Instrumentation
NMR spectra were recorded on Varian
300 or
500 MHz spectrometer
s
at 25
°
C. Chemical
shifts are referenced against the residual solvent signal for deuterated chloroform (
= 7.26 ppm).
SEC data were collected using two Agilent PLgel MIXED
-
B 300 × 7.5 mm columns with
10 μm beads, connected to an Agilent 1260 Series pump, a Wyatt 18
-
angle DAWN HELEOS light
scattering detector, and Optilab rEX differential refractive index detector. The mob
ile phase was
THF. Online determination of
dn
/
dc
assumed 100% mass elution under the peak of interest.
Reflection measurements were performed on a Cary 5000 UV/
Visible
/NIR
spectrophotometer, equipped with an ‘integrating sphere’ diffuse reflectance access
ory (Internal
DRA 1800). All measurements were referenced to a LabSphere Spectralon 99% certified
reflectance standard. Samples were illuminated through a Spectralon
-
coated aperture with a
diameter of 1 cm, with a beam area of approximately 0.5 cm
2
. The sa
mples were scanned at a rate
of 600 nm/min, with a 1 nm data interval, from 1800 to 200 nm, and with a detector crossover
(InGaAs to PMT) at 800 nm.
SAXS data was collected at Beamline 12
-
ID
-
B at Argonne National Laboratory’s
Advanced Photon Source
(AP
S)
. The samples were probed using 12 keV (1.033
Å
) X
-
rays, and
the sample
-
to
-
detector distance was approximately 2.3 m. WAXS data was collected at Beamline
5
-
ID
-
D at the APS. The samples were probed using 17 keV (0.726 Å) X
-
rays, and the sample
-
to
-
detecto
r distance was 8.5 m.
Scanning electron microscopy (SEM) was performed using a
FEI Nova 200 NanoLab
Dualbeam instrument operated at 5 kV. Samples were prepared by fracturing sample films
supported on glass to expose a cross
-
section, followed by staining ov
er
RuO
4
vapor for 3 minutes.
S
3
Synthesis of PDMS Macromonomer
Under air, a solution of
N
-
(hexanoic acid)
-
cis
-
5
-
norbornene
-
exo
-
dicarboximide
(6.00 g,
21.6 mmol), alcohol
-
terminated PDMS (18.1 g, 18.1 mmol,
M
n
= 1000 g/mol),
N
-
ethyl
-
N′
-
(3
-
dimethylaminopropyl)carbodiimide hydrochloride (
EDC
·
HCl, 5.52 g, 28.8 mmol), and
4
-
dimethylaminopyridine (
DMAP, 222 mg, 1.80 mmol) was prepared in 250 mL of
dichloromethane. After stirring for 20 hours at room temperature, the organic solution was washed
with 1 M aqueous HCl (3 × 75 mL), brine (3 × 75 mL), and deionized water (3 × 75 mL). The
organic solution was stirred over anhydrous MgSO
4
, filtered, and vol
atile components were
removed under vacuum. The product was filtered through a plug of silica with dichloromethane (2
L). Drying
in vacuo
allowed isolation of the PDMS macromonomer as a colorless oil (18.6 g,
82%).
1
H NMR (CDCl
3
, 300 MHz) δ 6.28 (s, 2H), 4
.20 (dd, 4H), 3.61 (dd, 4H), 3.44 (dt, 10H),
3.27 (t, 4H), 2.33 (t, 2H), 1.59 (m, 9H), 1.31 (m, 6H), 1.21 (d, 1H), 0.88 (t, 4H), 0.52 (td, 4H),
0.07(s, 104H).
M
n
(NMR) = 1280,
M
n
(SEC) = 1230,
Đ
= 1.03,
dn
/
dc
= 0.0385.
Synthesis of PTMC Macromonomer
Unde
r an argon atmosphere, a
solution of
N
-
(hydroxyethyl)
-
cis
-
5
-
norbornene
-
exo
-
2,3
-
dicarboximide (2.65 g, 12.8 mmol) and trimethylene carbonate (15.6 g, 154 mmol) was prepared
in 100 mL of dry dichloromethane.
D
ry
1,8
-
diazabicyclo[5.4.0]undec
-
7
-
ene (DBU,
1.00 mL,
6.70
mmol) was rapidly added by syringe. After stirring for 17 hours at 23 °C, benzoic acid (2.50
g
,
20.5 mmol) was
added,
and the solution was exposed to air. After removing volatile components
under reduc
ed pressure, the residual cloudy oil was washed with methanol (6 × 20 mL) and
methanol/dichloromethane (3:1 ratio, 6 × 20 mL), and dried
in vacuo
to isolate PTMC
macromonomer
as a viscous, colorless oil (16.69 g, 91%).
1
H NMR (CDCl
3
, 300 MHz) δ 6.28 (t,
2H
), 4.23 (t, 60H), 3.79 (t, 2H), 3.73 (t, 2H), 3.27 (t, 2H), 2.70 (d, 2H), 2.04 (p, 30H), 1.51 (dt,
2H), 1.29 (dt, 2H).
M
n
(NMR) = 1640,
M
n
(SEC) = 2220,
Đ
= 1.07,
dn
/
dc
= 0.0496.
N
O
O
OH
O
5
+
HO
O
Si
O
Si
C
4
H
9
11
EDC
ѣ
HCl,
DMAP
CH
2
Cl
2
N
O
O
O
O
O
Si
O
Si
C
4
H
9
11
5
N
O
O
O
O
O
H
O
12
CH
2
Cl
2
N
N
N
H
N
O
O
OH
+
O
O
O
S
4
Homopolymerization of PDMS Macromonomer
In a glovebox, a 20
-
mL
scintillation vial was charged with 31.9 mg of PDMS
macromonomer
(25.0 μmol
,
200 equiv), 985 μL of THF, and a stir bar. With rapid stirring, catalyst
G3
(0.125 μmol, 15 μL of a stock solution of 3.0 mg of
G3
in 0.500 mL of THF, 1 equiv) was
quickly added b
y syringe. After 30 minutes, the solution was exposed to air and quenched by
addition of ~0.1 mL of ethyl vinyl ether. Volatile components were removed under reduced
pressure. The oily residue was washed with methanol (3 mL) and dried under vacuum.
1
H NMR
(CDCl
3
, 500 MHz) δ 5.75 (br), 5.51 (br), 4.20 (t), 3.61 (m), 3.42 (m), 3.29 (br), 3.03 (br), 2.71 (br),
2.33 (m), 1.63 (m), 1.31 (m), 1.25 (t), 0.88 (t), 0.53 (m), 0.07 (m).
M
n
(SEC) = 2.32 x 10
5
,
Đ
=
1.05,
dn
/
dc
= 0.0385.
Homopolymerization of PTMC
Macromonomer
In a glovebox, a 20
-
mL scintillation vial was charged with 40.7 mg of PTMC
macromonomer (25.0 μmol
,
200 equiv), 985 μL of THF, and a stir bar. With rapid stirring, catalyst
G3
(0.125 μmol, 15 μL of a stock solution of 3.0 mg of
G3
in 0.500 mL
of THF, 1 equiv) was
quickly added via syringe. After 30 minutes, the solution was exposed to air and quenched by
addition of ~0.1 mL of ethyl vinyl ether. Volatile components were removed under reduced
pressure. The white residue was washed with methanol
(3 mL) and dried under vacuum.
1
H NMR
(CDCl
3
, 500 MHz) δ 5.81 (br), 5.55 (br), 4.35 (t), 4.29 (t), 3.80 (m), 3.34 (br), 3.11 (br), 2.77 (br),
2.11 (p), 1.97 (p).
M
n
(SEC) = 4.83 x 10
5
,
Đ
= 1.18,
dn
/
dc
= 0.0581.
Synthesis of PDMS
b
PTMC Brush Block Polyme
rs
In a glovebox, a 20
-
mL scintillation vial was charged with a stir bar, PDMS
macromonomer (191 mg, 150 μmol), and 6.0 mL of THF. While rapidly stirring, an appropriate
quantity of a solution of
G3
(34.3 mM) in THF was quickly added by syringe. After 20 minu
tes,
a small aliquot (<0.1 mL) of the solution was extracted by syringe and quenched with ethyl vinyl
ether for subsequent SEC analysis. After collection of the aliquot, a solution of PTMC
macromonomer (245 mg, 150 μmol) in 6.0 mL of THF was added to the r
eaction vial. After 1
hour, a second aliquot (<0.1 mL) for SEC analysis was collected. The reaction vial was removed
from the glovebox and quenched by addition of 0.25 mL of ethyl vinyl ether. The sample was
concentrated to ~5 mL by rotary evaporation, and
the solution was added dropwise to cold
methanol (
78 °C). The supernatant was removed, and the sample was dried in vacuo for 48 hours
to yield PDMS
b
PTMC as a rubbery white solid.
N
O
O
O
O
O
H
O
12
N
O
O
O
O
O
Si
O
Si
C
4
H
9
11
5
N
O
O
O
O
O
H
O
12
N
O
O
O
O
O
Si
O
Si
C
4
H
9
11
5
n
n
+
1)
2)
n
n
Ru
Cl
Cl
Ph
N
N
N
N
Mes
Mes
G3
THF, 25
°
C
PDMS
PTMC
PDMS
n
-
b
-PTMC
n
S
5
Table S1.
Brush
b
lock
p
olymerization of PDMS and PTMC macromonomers by
G
3
.
Entry
[PDMS]:[PTMC]:[
G3
]
M
n
Expected
(kDa)
a
M
n
measured
(kDa)
b
f
PDMS
c
Đ
d
1
100:100:1
291
290
0.52
1.12
2
150:150:1
437
423
0.53
1.17
3
200:200:1
582
564
0.52
1.18
4
250:250:1
728
684
0.53
1.19
5
300:300:1
873
815
0.52
1.22
a
Based on the
monomer/
G3
ratio.
b
Based on a combination of light scattering and
1
H NMR
measurements.
c
Calculated assuming a PDMS density of .985 g/mL
5
and a PTMC density of 1.31
g/mL
6
.
d
Determined by SEC light scattering detector.
NMR Spectra
Figure S1.
1
H NMR spectrum of PDMS macromonomer
(CDCl
3
solvent).
0
.
0
0
.
5
1
.
0
1
.
5
2
.
0
2
.
5
3
.
0
3
.
5
4
.
0
4
.
5
5
.
0
5
.
5
6
.
0
6
.
5
7
.
0
p
p
m
C
D
C
l
3
C
H
2
C
l
2
C
H
3
O
H
0
.
0
5
0
.
1
0
p
p
m
S
6
Figure S2.
1
H NMR spectrum of PTMC macromonomer (CDCl
3
solvent).
Figure S3.
1
H NMR spectrum of
g
-
PDMS homopolymer (CDCl
3
solvent).
1
.
2
1
.
4
1
.
6
1
.
8
2
.
0
2
.
2
2
.
4
2
.
6
2
.
8
3
.
0
3
.
2
3
.
4
3
.
6
3
.
8
4
.
0
4
.
2
4
.
4
4
.
6
4
.
8
5
.
0
5
.
2
5
.
4
5
.
6
5
.
8
6
.
0
6
.
2
6
.
4
6
.
6
6
.
8
7
.
0
7
.
2
7
.
4
7
.
6
p
p
m
C
D
C
l
3
C
H
2
C
l
2
C
H
3
O
H
0
.
0
0
.
5
1
.
0
1
.
5
2
.
0
2
.
5
3
.
0
3
.
5
4
.
0
4
.
5
5
.
0
5
.
5
6
.
0
6
.
5
7
.
0
7
.
5
p
p
m
C
H
C
l
3
T
H
F
T
H
F