1
Supporting Information
Universal Relationship between Conductivity and Sol
vation-Site
Connectivity Ether-based Polymer Electrolytes
Danielle M. Pesko,
†1
Michael A. Webb,
‡1
Yukyung Jung,
∥
1
Qi Zheng,
∥
Thomas F. Miller III,
‡
*
Geoffrey W. Coates,
∥
* and Nitash P. Balsara
†,§,┴
*
†
Department of Chemical and Biomolecular Engineering
, University of California, Berkeley,
California 94720, USA
‡
Division of Chemistry and Chemical Engineering, Cal
ifornia Institute of Technology, Pasadena,
California 91125, USA
∥
Department of Chemistry and Chemical Biology, Baker
Laboratory, Cornell University, Ithaca, New
York 14853, USA
§
Materials Science Division, Lawrence Berkeley Natio
nal Laboratory, Berkeley, California 94720,
USA
┴
Environmental Energy Technology Division, Lawrence
Berkeley National Laboratory, Berkeley,
California 94720, USA
1
These authors contributed equally to the work.
2
Contents
1 Synthesis Details .............................
...................................................
..................................................
4
1.1 General Considerations ......................
...................................................
........................................ 4
1.2 Materials....................................
...................................................
................................................. 4
1.3 Synthesis of Monomers .......................
...................................................
....................................... 5
1.3.1 Synthesis of C
2
EO
4
π
Monomer ..........................................
...................................................
5
1.3.2 Synthesis of C
2
EO
5
π
Monomer ..........................................
...................................................
6
1.3.3 Synthesis of C
4
EO
4
π
Monomer ..........................................
...................................................
6
1.3.4 Synthesis of C
4
EO
5
π
Monomer ..........................................
...................................................
7
1.3.5 Synthesis of C
6
EO
4
π
Monomer ..........................................
...................................................
8
1.3.6 Synthesis of C
6
EO
5
π
Monomer ..........................................
...................................................
9
1.4 Synthesis of Polymers .......................
...................................................
......................................... 9
1.4.1 Representative ADMET Procedure for Unsatura
ted Polyethers ....................................
........ 9
1.4.2 Synthesis of Unsaturated [C
2
EO
5
π
]
n
Polymer ..........................................
........................... 10
1.4.3 Synthesis of Unsaturated [C
4
EO
4
π
]
n
Polymer ..........................................
........................... 10
1.4.4 Synthesis of Unsaturated [C
4
EO
5
π
]
n
Polymer ..........................................
........................... 10
1.4.5 Synthesis of Unsaturated [C
6
EO
4
π
]
n
Polymer ..........................................
............................ 11
1.4.6 Synthesis of Unsaturated [C
6
EO
5
π
]
n
Polymer ..........................................
............................ 11
1.4.7 Representative Hydrogenation Procedure ....
...................................................
...................... 11
1.4.8 Procedure for Removal of Ruthenium Residues
from Polymer .....................................
..... 12
1.5 NMR Spectra of Polymers .....................
...................................................
.................................. 13
1.5.1 NMR Spectra of Unsaturated [C
2
EO
4
π
]
n
..................................................
........................... 13
1.5.2 NMR Spectra of [C
2
EO
4
]
n
..................................................
..................................................
15
1.5.3 NMR Spectra of Unsaturated [C
2
EO
5
π
]
n
..................................................
........................... 16
1.5.4 NMR Spectra of [C
2
EO
5
]
n
..................................................
..................................................
17
1.5.5 NMR Spectra of Unsaturated [C
4
EO
4
π
]
n
..................................................
........................... 18
1.5.6 NMR Spectra of [C
4
EO
4
]
n
..................................................
..................................................
19
1.5.7 NMR Spectra of Unsaturated [C
4
EO
5
π
]
n
..................................................
........................... 20
1.5.8 NMR Spectra of [C
4
EO
5
]
n
..................................................
..................................................
21
1.5.9 NMR Spectra of Unsaturated [C
6
EO
4
π
]
n
..................................................
........................... 22
1.5.10 NMR Spectra of [C
6
EO
4
]
n
...................................................
............................................... 23
1.5.11 NMR Spectra of Unsaturated [C
6
EO
5
π
]
n
..................................................
......................... 24
1.5.12 NMR Spectra of [C
6
EO
5
]
n
...................................................
............................................... 25
3
1.6 Analysis of Polymer Endgroups ...............
...................................................
................................ 26
1.7 Analysis of Polymer Thermal Stability .......
...................................................
............................. 28
1.7.1 Representative TGA Thermograms ............
...................................................
....................... 28
2 Force Field Parameters for Molecular Dynamics S
imulations ........................................
.................. 29
2.1 NonBbonded Interaction Parameters............
...................................................
............................. 29
2.2 Bonding Potential Parameters ................
...................................................
.................................. 30
2.3 Bending Potential Parameters ................
...................................................
.................................. 30
2.3 Torsional Potential Parameters ..............
...................................................
................................... 31
3 Derivation of
f
exp
Formula ..........................................
...................................................
..................... 32
4 Electrolyte Characterization at Different Salt
Concentrations ....................................
....................... 34
5 Approximating Conductivity Using the Universal
Equation ..........................................
................... 35
5.1 Tabulated Data for
σ
and
T
g
of PEO ...........................................
................................................. 3
6
5.2 Approximating the
T
g
of a Polyether Electrolyte .......................
................................................. 3
6
6 References ....................................
...................................................
...................................................
38
4
1 Synthesis Details
1.1 General Considerations
All manipulation of air and water sensitive compoun
ds were carried out under dry nitrogen
using a Braun Labmaster Glovebox or standard Schlen
k line techniques.
1
H and
13
C NMR spectra were
recorded on Varian INOVA 400 (
1
H, 400 MHz) or Varian INOVA 500 (
1
H, 500 MHz) spectrometers.
1
H
NMR spectra were referenced with residual nonBdeute
rated solvent shifts (CHCl
3
=7.26 ppm), and
13
C
NMR spectra were referenced by the deuterated solve
nt shifts (CDCl
3
=77.16 ppm).
Flash column chromatography was performed using si
lica gel with particle size 40B64 Jm, 230B
400 mesh. Gel permeation chromatography (GPC) analy
ses were done using an Agilent PLBGPC 50
integrated system (2 x Plgel MiniBMIX C columns, 5
micron, 4.6 mmID) equipped with a refractive
index detector. The GPC columns were eluted with te
trahydrofuran at a rate of 0.3 mL/min at 30 ºC,
and calibration was done using monodisperse polysty
rene standards.
Differential Scanning Calorimetry (DSC) of polymer
samples was performed on a TA
Instruments Q1000 modulated differential scanning c
alorimeter with a 50 chamber autosampling
platform. Samples were prepared in crimped aluminum
pans, and experiments were conducted using
the following protocol unless otherwise stated: hea
ting under nitrogen from 25 ºC to 200 ºC at 10
ºC/min, cooling from 200 to B100 ºC at 10 ºC/min, a
nd then heating from B100 to 200 ºC at 10 ºC/min.
The data were processed using Universal Analysis 20
00 software, and all reported glass transition
temperatures (
T
g
) and melting temperatures (
T
m
) were obtained from the second heating cycle. Ther
mal
gravimetric analysis (TGA) was performed using a TA
Instruments Q500 Thermogravimetric Analyzer
equipped with an autosampler. HRMS Analyses were pe
rformed on a Thermo Scientific Exactive
Orbitrap MS system with an Ion Sense DART ion sourc
e.
1.2 Materials
Grubbs first generation catalyst (SigmaBAldrich or
Strem) and Crabtree’s catalyst (SigmaB
5
Aldrich) were stored under nitrogen in the glovebox
and used as received. Diethylene glycol (SigmaB
Aldrich, 99%) was dried over activated 3 Å molecula
r sieves overnight then vacuum distilled.
Triethylene glycol (SigmaBAldrich, 99%) and tetraet
hylene glycol (SigmaBAldrich, 99%) were dried
over activated 3 Å molecular sieves overnight. Tetr
ahydrofuran (THF) and dichloromethane (DCM)
were obtained from Fisher Scientific and dimethylfo
rmamide (DMF) was obtained from Burdick and
Jackson, and the solvents were dried using a Phoeni
x solvent drying system. Alumina beads (FB200,
BASF) were activated by heating to 180 °C overnight
under reduced pressure, then stored in the
glovebox. All other reagents were purchased from co
mmercial sources and used as received.
1.3 Synthesis of Monomers
1.3.1 Synthesis of C
2
EO
4
π
Monomer
In the glovebox, sodium hydride (95%, 2.7 g, 112 mm
ol) was added to a 500 mL vacuumB
adapted round bottom flask with a stirbar. The flas
k was sealed and taken out of the glovebox, and THF
(200 mL) was added via cannula under nitrogen. Trie
thylene glycol (6.0 mL, 44 mmol) was added
dropwise and stirred for 20 minutes at room tempera
ture. Allyl bromide (8.0 mL, 92.4 mmol) was
added dropwise, and the reaction was stirred overni
ght. The reaction was concentrated in vacuo, and
the residue was suspended in 150 mL of ether. The e
ther layer was washed three times with water, dried
over magnesium sulfate, and concentrated. The crude
product was purified by column chromatography
using 50% ether in hexanes as the eluent. The produ
ct was obtained in 57% yield (5.76 g, 25.0 mmol),
and stored neat over activated alumina beads in the
glovebox. The
1
H NMR spectrum of the product
matched well with literature values.
1
1
H NMR spectrum in ppm (CDCl
3
, 500 MHz): δ 5.97B5.84 (ddt,
J
=5.7 Hz, 5.7 Hz, 10.5Hz, 21.9 Hz, 2H); 5.26 (dd, J=
1.6 Hz, 17.2 Hz, 2H); 5.17 (dd, J=1.24 Hz, 10.4
Hz, 2H); 4.01 (d, J=2.7 Hz, 4H); 3.71B3.50 (m, 12 H
).
13
C NMR spectrum in ppm (CDCl
3
, 125 MHz): δ
134.88, 117.22, 72.36, 70.76, 69.54. HR/MS (DART):
calculated for C
12
H
23
O
4
+
(M+H)
+
231.1591
g/mol; found 231. 1590 g/mol.
6
1.3.2 Synthesis of C
2
EO
5
π
Monomer
Tetraethylene glycol diallyl ether was synthesized
following a procedure adapted from the
literature.
2
In the glovebox, sodium hydride (1.24 g, 51.5 mmol
) was added to a 100 mL round bottom
flask with a stirbar. The flask was removed from th
e glovebox, and 20 mL of dry degassed DMF was
added via syringe. The flask was cooled to 0 ̊C, an
d tetraethylene glycol was added dropwise (2.0 g,
10.3 mmol). The reaction was stirred at 0 ̊C for 15
minutes, then allyl glycidyl ether (3.48 mL, 40.2
mmol) was added dropwise. The flask was warmed to r
oom temperature and stirred overnight. The
reaction was quenched with isopropanol, filtered th
rough a Celite plug, and diluted with ~100 mL ether.
The solution was washed three times with brine, dri
ed over sodium sulfate, and concentrated. The
crude product was purified by column chromatography
with 100% diethyl ether as the eluent. The
product was obtained in 77% yield (2.18 g, 7.9 mmol
), and stored neat over activated alumina beads in
the glovebox.
1
H NMR spectrum in ppm (CDCl
3
, 500 MHz): δ 5.90 (ddd, J=5.7 Hz, 10.9 Hz, 22.8 Hz
,
2H); 5.26 (dd, J=1.3 Hz, 17.2 Hz, 2H); 5.17 (d, J=1
0.4 Hz, 2H); 4.01 (d, J=5.7 Hz, 4H); 3.75B3.52 (m,
1H).
13
C NMR spectrum in ppm (CDCl
3
, 125 MHz): δ 134.88, 117.22, 72.36, 70.76, 70.72,
69.54.
HR/MS (DART): calculated for C
14
H
27
O
5
+
(M+H)
+
275.1853 g/mol; found 275.1850 g/mol.
1.3.3 Synthesis of C
4
EO
4
π
Monomer
The synthesis of the mesylBterminated PEG was adapt
ed from a literature procedure.
3
Triethylene glycol (3 g, 20 mmol) was added to a 30
0 mL vacuum adapted round bottom flask
equipped with a stirbar under nitrogen. Dry dichlor
omethane (100 mL) and diisopropylethylamine (7.7
mL, 44 mmol) were added via cannula, and the flask
was cooled to 0 ̊C. The solution was stirred for
10 minutes, and then methanesulfonyl chloride (3.4
mL, 44 mmol) was added. The flask was allowed
to warm to room temperature and stirred overnight.
The crude reaction mixture was washed with 100
mL brine, and the organic layer was concentrated un
der reduced pressure. The residue was partitioned
between 100 mL hexanes and 100 mL water. Sodium chl
oride (10 g) was added to the aqueous layer,
7
which was extracted with 3x100 mL dichloromethane.
The combined organic layers were dried over
sodium sulfate and concentrated. The crude product
was purified by column chromatography using 5%
methanol in dichloromethane as the eluent. The prod
uct was isolated as a yellow oil in 29% yield (1.77
g, 5.8 mmol), and the
1
H NMR spectrum was consistent with the literature.
1
H NMR spectrum in ppm
(CDCl
3
, 400 MHz): δ4.37 (m, 4H), 3.76 (m, 4H), 3.67 (s, 4
H), 3.07 (s, 6H).
In the glovebox, sodium hydride (95%, 253 mg, 10.5
mmol) was added to a 20 mL scintillation
vial equipped with a stirbar. The vial was sealed w
ith a pierceable TeflonBlined septum cap and brough
t
out of the glovebox. Dry THF (5 mL) was added via s
yringe .The reaction was cooled to 0 ̊C, then 3B
buteneB1Bol (800 JL, 9.3 mmol) was added dropwise a
nd stirred for 15 minutes. The mesylBterminated
PEG (1.48 g, 4.8 mmol) was dissolved in 5 mL THF, a
nd the solution was added to the vial dropwise.
The reaction was warmed to room temperature and sti
rred overnight. The vial was quenched with H
2
O
and concentrated under reduced pressure. Diethyl et
her (80 mL) was added to the residue, and the
milky suspension was filtered through Celite and co
ncentrated. The crude product was purified by
column chromatography using 50% ether in hexanes as
the eluent. The product was isolated as a clear
oil in 36% yield (0.90 g, 1.7 mmol), and stored ove
r activated alumina beads in the glovebox.
1
H NMR
spectrum in ppm (CDCl
3
, 500 MHz): δ 5.82 (ddt, J=6.8 Hz, 6.8 Hz, 10.2 Hz,
17.0 Hz, 2H); 5.09 (dd,
J=1.5 Hz, 17.2 Hz, 2 H); 5.04 (d, J=10.2 Hz, 2H); 3
.70B3.58 (m, 12 H); 3.53 (t, J=6.9 Hz, 4H); 2.35 (q
,
J=6.8 Hz, 4H).
13
C NMR spectrum in ppm (CDCl
3
, 125 MHz): δ 135.27, 116.44, 70.77, 70.75, 70.70,
70.26, 34.25. HR/MS (DART): calculated for C
14
H
27
O
4
+
(M+H)
+
259.1909 g/mol; found 259.1903
g/mol.
1.3.4 Synthesis of C
4
EO
5
π
Monomer
The C
4
EO
5
π
monomer was synthesized using the same procedure a
s for C
4
EO
4
π
, except
tetraethylene glycol was used instead of triethylen
e glycol. The monomer was purified by column
chromatography using 50 to 75% ether in hexanes as
the eluent. The product was isolated as a clear oil
8
in 46% yield (0.66 g, 1.44 mmol), and stored over a
ctivated alumina beads in the glovebox.
1
H NMR
spectrum in ppm (CDCl
3
, 500 MHz): δ 5.81(ddt, J=6.7 Hz, 6.7 Hz, 10.2 Hz,
17.0 Hz, 2H); 5.08 (dd,
J=1.8 Hz, 17.2 Hz, 2H); 5.02 (d, J=10.2 Hz, 2H); 3.
68B3.56 (m, 18 H); 3.51 (t, J=6.9 Hz, 4H), 2.34 (qd
,
J=5.6 Hz, 6.8 Hz, 6.9 Hz, 6.9 Hz, 4H).
13
C NMR spectrum in ppm (CDCl
3
, 125 MHz): δ 135.27,
116.46, 70.78, 70.74, 70.72, 70.70, 70.26, 34.25. H
R/MS (DART): calculated for C
16
H
31
O
5
+
(M+H)
+
303.2166 g/mol; found 303.2165 g/mol.
1.3.5 Synthesis of C
6
EO
4
π
Monomer
The synthesis of the C
6
EO
4
π
monomer was adapted from a literature procedure.
4
In the
glovebox, sodium hydride (95%, 288 mg, 12 mmol) was
added to a 20 mL scintillation vial equipped
with a stirbar. The vial was sealed with a pierceab
le TeflonBlined septum cap and brought out of the
glovebox. Under nitrogen, sodium iodide (37 mg, 0.2
4 mmol) and dry THF (5 ml) were added (mg,
mmol), and the vial was cooled to 0 ̊C. Triethylene
glycol (0.54 mL, 4.0 mmol) was added dropwise,
and the reaction was stirred until the bubbling cea
sed (~5 minutes). The 5BbromoB1Bpentene (1.42 mL,
12 mmol) was added dropwise as a solution in 6 mL T
HF. The reaction was allowed to warm to room
temperature and stirred 5 days. The crude reaction
mixture was concentrated under reduced pressure.
The residue was diluted in 10 mL diethyl ether, fil
tered through Celite, and concentrated. The crude
product was purified by column chromatography using
33 to 50% diethyl ether in hexanes as the
eluent. The product was obtained as a clear oil in
31% yield (354 mg, 1.24 mmol) and stored over
activated alumina beads in the glovebox.
1
H NMR spectrum in ppm (CDCl
3
, 500 MHz): δ 5.82 (ddt,
J=6.6 Hz, 6.6 Hz, 10.2 Hz, 16.9 Hz, 2H); 5.03 (dd,
J=1.64 Hz, 17.1 Hz, 2H); 4.97 (d, J=10.2 Hz, 2H);
3.70B3.57 (m, 8H); 3.48 (t, J=6.7 Hz, 4H); 2.12 (dd
, J=7.3 Hz, 14.3 Hz, 4H); 1.69 (m, 4H).
13
C NMR
spectrum in ppm (CDCl
3
, 125 MHz): δ 138.43, 114.81, 70.84, 70.76, 70.24,
30.37, 28.91. HR/MS
(DART): calculated for C
16
H
31
O
4
+
(M+H)
+
287.2217 g/mol; found 287.2215 g/mol.
9
1.3.6 Synthesis of C
6
EO
5
π
Monomer
The C
6
EO
5
π
monomer was synthesized using the same procedure a
s for C
6
EO
4
π
, except
tetraethylene glycol was used instead of triethylen
e glycol. The crude product was purified by column
chromatography using 50 to 75% ether in hexanes as
the eluent. The product was isolated as a clear oil
in 35% yield (459 mg, 1.4 mmol), and stored over ac
tivated alumina beads in the glovebox.
1
H NMR
spectrum in ppm (CDCl
3
, 500 MHz): δ 5.80 (ddt, J=6.6 Hz, 6.6 Hz, 10.2 Hz,
13.3 Hz, 2 H); 5.00 (d,
J=17.1 Hz, 2H); 4.94 (d, J=10.1 Hz, 2H); 3.78B3.52
(m, 12H); 3.45 (t, J=6.7 Hz, 4H); 2.10 (dd, J=7.0
Hz, 14.3 Hz, 4H); 1.67 (m, 4H).
13
C NMR spectrum in ppm (CDCl
3
, 125 MHz): δ 138.41, 114.81,
70.83, 7074, 70.23, 30.36, 28.90. HR/MS (DART): cal
culated for C
18
H
35
O
5
+
(M+H)
+
331.2479 g/mol;
found 331.2477 g/mol.
1.4 Synthesis of Polymers
1.4.1 Representative ADMET Procedure for Unsatura
ted Polyethers
In the glovebox, Grubbs first generation catalyst (
11.2 mg, 13.6 Jmol) was added to a 100 mL
vacuumBadapted round bottom flask equipped with a 1
' stirbar. Neat triethylene glycol diallyl ether
(C
2
EO
4
π
,
200 mg, 0.87 mmol) was added via Pasteur pipet. Dry
, degassed dichloromethane (~0.5 mL)
was used to rinse the sides of the flask and pipet.
The flask was sealed and brought outside of the
glovebox. On the Schlenk line, the dichloromethane
was removed under reduced pressure at room
temperature while stirring. After ~1 minute, the rea
ction was left open to vacuum and heated to 50 ̊C
for 2 hours. The polymerization was quenched by coo
ling the reaction to room temperature under
nitrogen, then rapidly adding 0.5 mL ethyl vinyl et
her via syringe. The reaction was then stirred at
room temperature for at least 30 minutes before pre
cipitating into 15 mL of stirring hexanes. The
hexanes were decanted from the precipitated polymer
, which was dried at room temperature under
reduced pressure. The polymer was isolated as a bro
wn tacky goo in 87% yield.
10
1.4.2 Synthesis of Unsaturated [C
2
EO
5
π
]
n
Polymer
The unsaturated [C
2
EO
5
π
]
n
polymer was synthesized by following the represent
ative ADMET
procedure with the C
2
EO
5
π
monomer (400 mg, 1.5 mmol) and Grubbs first genera
tion catalyst (19.2
mg, 23.3 Jmol). The polymerization was run for 2 ho
urs at 50 ̊C under reduced pressure, and the
polymer was precipitated in hexanes and isolated as
a brown goo in 64% yield (231.0 mg).
1.4.3 Synthesis of Unsaturated [C
4
EO
4
π
]
n
Polymer
In the glovebox, Grubbs first generation catalyst (
10.2 mg, 12.4 Jmol) was added to a 100 mL
vacuumBadapted round bottom flask equipped with a 1
' stirbar. Neat C
4
EO
4
π
monomer (200 mg, 0.77
mmol) was added via Pasteur pipet. Dry, degassed di
chloromethane (~0.5 mL) was used to rinse the
sides of the flask and pipet. The flask was sealed
and brought outside of the glovebox. On the Schlenk
line, the dichloromethane was removed under reduced
pressure at room temperature while stirring.
After ~1 minute, the reaction was left open to vacuu
m and heated to 50 ̊C for 2 hours. After 2 hours, a
solution of Grubbs first generation catalyst (1.3 m
g, 1.6 Jmol) in 0.5 mL dry, degassed
dichloromethane was added via syringe under nitroge
n, and the polymerization was continued for 2
hours at 50 ̊C under vacuum. The polymerization was
quenched by cooling the reaction to room
temperature under nitrogen, then rapidly adding 0.5
mL ethyl vinyl ether via syringe. The reaction was
then stirred at room temperature for at least 30 mi
nutes before precipitating into 15 mL of stirring
hexanes. The hexanes were decanted from the precipi
tated polymer, which was dried at room
temperature under reduced pressure. The polymer was
isolated as a brown goo in 71% yield (125.8
mg).
1.4.4 Synthesis of Unsaturated [C
4
EO
5
π
]
n
Polymer
The unsaturated [C
4
EO
5
π
]
n
polymer was synthesized following the same procedu
re as for the
unsaturated [C
4
EO
4
π
]
n
polymer, except using the C
4
EO
5
π
monomer (200 mg, 0.66 mmol) and Grubbs
first generation catalyst (8.7 mg, 10.6 Jmol), foll
owed by a second addition of Grubbs catalyst in 0.5
11
mL dichloromethane after 2 hours (1.3 mg, 1.6 Jmol)
. The reaction was quenched with ethyl vinyl
ether 2 hours after the second addition of catalyst
and stirred for at least 30 minutes. The polymer w
as
isolated as a brown goo in 81% yield (147.4 mg).
1.4.5 Synthesis of Unsaturated [C
6
EO
4
π
]
n
Polymer
In the glovebox, Grubbs first generation catalyst (
10.3 mg, 12.5 Jmol) was added to a 100 mL
vacuumBadapted round bottom flask equipped with a 1
' stirbar. Neat C
6
EO
4
π
monomer (220 mg, 0.77
mmol) was added via Pasteur pipet. Dry, degassed di
chloromethane (~0.5 mL) was used to rinse the
sides of the flask and pipet. The flask was sealed
and brought outside of the glovebox. On the Schlenk
line, the dichloromethane was removed under reduced
pressure at room temperature while stirring.
After ~1 minute, the reaction was left open to vacuu
m and heated to 50 ̊C for 1 hour. The
polymerization was quenched by cooling the reaction
to room temperature under nitrogen, then rapidly
adding 0.5 mL ethyl vinyl ether via syringe. The re
action was then stirred at room temperature for at
least 30 minutes before precipitating into 15 mL of
stirring hexanes. The hexanes were decanted from
the precipitated polymer, which was dried at room t
emperature under reduced pressure. The polymer
was isolated as a brown tacky goo in 56% yield (109
.0 mg).
1.4.6 Synthesis of Unsaturated [C
6
EO
5
π
]
n
Polymer
The unsaturated [C
6
EO
5
π
]
n
polymer was synthesized following the same procedu
re as for the
unsaturated [C
6
EO
4
π
]
n
except using the C
6
EO
5
π
monomer (220 mg, 0.66 mmol) with Grubbs first
generation catalyst (9.0 mg, 10.9 Jmol). The polyme
rization was run for 1 hour, quenched with ethyl
vinyl ether, and precipitated in hexanes. The polym
er was isolated as a brown tacky goo in 78% yield
(156.7 mg).
1.4.7 Representative Hydrogenation Procedure
In the glovebox, unsaturated [C
2
EO
4
π
]
n
polymer (from C
2
EO
4
π
monomer, 600 mg unsaturated
12
polymer, 3.0 mmol repeat units) and Crabtree's cata
lyst (52 mg, 65 μmol) were dissolved in 100 mL
dry dichloromethane. The solution was added to a Fi
scherBPorter bottle with a stirbar, and the reactor
head was attached. The FischerBPorter bottle was re
moved from the glovebox and charged with 30 psig
of hydrogen. The reaction was stirred at room tempe
rature for 20 hours, and then the reactor was
vented to atmospheric pressure. The solvent was rem
oved under reduced pressure to yield the
hydrogenated polymer as a brownish grey tacky goo i
n quantitative yield.
1.4.8 Procedure for Removal of Ruthenium Residues
from Polymer
The procedure for removing residual Ru was adapted
from a literature procedure.
5
The polymer
was dissolved in dichloromethane to give a concentr
ation of ~50 mg/mL. Activated carbon (Darco KB
100 mesh wet powder, SigmaBAldrich) was added (100
mass % relative to polymer), and the
suspension was stirred at room temperature overnigh
t. The slurry was filtered through a plug of
Whatman glass microfiber filter paper cotton wool,
and then concentrated under reduced pressure.
13
1.5 NMR Spectra of Polymers
1.5.1 NMR Spectra of Unsaturated [C
2
EO
4
π
]
n
1
H NMR spectrum in ppm (CDCl
3
, 400 MHz): δ 6.27 (dd,
J
=29.8, 12.6 Hz, endgroup); 5.85B
5.75 (m,
trans
alkene, 2H including
cis
alkene); 5.73B5.67 (m,
cis
Balkene); 4.80B4.67 (m, endgroup);
4.10B3.95 (m, 4H); 3.71B3.51 (m, 13 H); 2.18 (q,
J
=7.2, 7.2, 7.2 Hz, endgroup); 1.53 (dd,
J
=6.7, 1.5 Hz,
endgroup).
13
C NMR spectrum in ppm (CDCl
3
, 125 MHz): δ 129.66, 129.49, 71.32, 70.72, 69.66,
69.59, 66.99, 28.37 (endgroup).
Figure 1.
1
H NMR spectrum of unsaturated [C
2
EO
4
π
]
n
polymer in CDCl
3
.
14
Figure 2.
13
C NMR spectrum of unsaturated [C
2
EO
4
π
]
n
polymer in CDCl
3
.
15
1.5.2 NMR Spectra of [C
2
EO
4
]
n
1
H NMR spectrum in ppm (CDCl
3
, 500 MHz): δ 3.70B3.51 (m, 12 H); 3.50B3.40 (m, 4H
); 1.69B
1.56 (m, 4H); 0.90 (t,
J
=7.4, 7.4 Hz, endgroup).
13
C NMR spectrum in ppm (CDCl
3
, 125 MHz): δ
71.26, 70.73, 70.19 26.39.
Figure 3.
1
H NMR spectrum of [C
2
EO
4
]
n
polymer in CDCl
3
.
Figure 4.
13
C NMR spectrum of [C
2
EO
4
]
n
polymer in CDCl
3
.
16
1.5.3 NMR Spectra of Unsaturated [C
2
EO
5
π
]
n
1
H NMR spectrum in ppm (CDCl
3
, 500 MHz): δ 5.89 (ddt,
J
=17.2, 10.4, 5.7 Hz, endgroup);
5.79B5.75 (m,
trans
alkene, 2H including
cis
alkene); 5.70B5.67 (m,
cis
Balkene); 5.27B5.12 (m,
endgroup); 4.10B3.93 (m, 4H); 3.73B3.47 (m, 18H); 1
.52 (dd,
J
= 6.7, 1.6 Hz, endgroup).
13
C NMR
spectrum in ppm (CDCl
3
, 125 MHz): δ 129.59, 71.26, 70.71, 70.70, 70.67, 6
9.65, 69.59, 66.97.
Figure 5.
1
H NMR spectrum of unsaturated [C
2
EO
5
π
]
n
polymer in CDCl
3
.
Figure 6.
13
C NMR spectrum of unsaturated [C
2
EO
5
π
]
n
in CDCl
3
.
17
1.5.4 NMR Spectra of [C
2
EO
5
]
n
1
H NMR spectrum in ppm (CDCl
3
, 500 MHz): δ 3.70B3.53 (m, 19H); 3.50B3.42 (m, 4H)
; 1.68B
1.56 (m, 4H); 0.89 (t,
J
=7.4, 7.4 Hz, endgroup).
13
C NMR spectrum in ppm (CDCl
3
, 125 MHz): δ
71.28, 70.78, 70.24, 26.44
.
Figure 7.
1
H NMR spectrum of [C
2
EO
5
]
n
polymer in CDCl
3
.
Figure 8.
13
C NMR spectrum of [C
2
EO
5
]
n
polymer in CDCl
3
.
18
1.5.5 NMR Spectra of Unsaturated [C
4
EO
4
π
]
n
1
H NMR spectrum in ppm (CDCl
3
, 500 MHz): δ 5.87B5.76 (m, endgroup); 5.53B5.41 (m
, 2H);
5.13B4.97 (m, endgroup); 3.69B3.56 (m, 13H); 3.46 (
td,
J
= 7.1, 1.5 Hz, 4H); 2.35 (dd,
J
= 12.7, 7.1 Hz,
2H); 2.28 (dt,
J
= 7.1, 6.3 Hz, 2H).
13
C NMR spectrum in ppm (CDCl
3
, 125 MHz): δ 128.50, 127.64,
71.26, 70.98, 70.75, 70.73, 70.71, 70.28, 70.21, 33
.18, 28.12.
Figure 9.
1
H NMR spectrum of unsaturated [C
4
EO
4
π
]
n
polymer in CDCl
3
.
Figure 10.
13
C NMR spectrum of unsaturated [C
4
EO
4
π
]
n
polymer in CDCl
3
.
19
1.5.6 NMR Spectra of [C
4
EO
4
]
n
1
H NMR spectrum in ppm (CDCl
3
, 400 MHz): δ 3.68 – 3.53 (m, 12H); 3.43 (t,
J
= 6.7 Hz, 4H);
1.87 (br s, endgroup); 1.62 – 1.51 (m, 4H); 1.39 –
1.27 (m, 4H); 0.90 (t,
J
= 7.4 Hz, endgroup).
13
C
NMR spectrum in ppm (CDCl
3
, 125 MHz): δ 71.54, 70.73, 70.72, 70.18, 29.72, 26
.10.
Figure 11.
1
H NMR spectrum of [C
4
EO
4
]
n
polymer in CDCl
3
.
Figure 12.
13
C NMR spectrum of [C
4
EO
4
]
n
polymer in CDCl
3
.
20
1.5.7 NMR Spectra of Unsaturated [C
4
EO
5
π
]
n
1
H NMR spectrum in ppm (CDCl
3
, 400 MHz): δ 5.88B5.75 (m, endgroup); 5.53B5.40 (m
, 2H);
5.14B4.98 (m, endgroup); 3.66B3.55 (m, 17H); 3.45 (
td,
J
= 7.1, 1.5 Hz, 4H); 2.34 (dd,
J
= 12.7, 7.0 Hz,
2H); 2.28 (ddd,
J
= 10.8, 7.0, 1.4 Hz, 1H), 1.70 (dd,
J
= 6.3, 1.3 Hz, endgroup).
13
C NMR spectrum in
ppm (CDCl
3
, 125 MHz): δ 128.48, 127.63, 71.25, 70.97, 70.71,
70.26, 70.20, 33.16, 28.10.
Figure 13.
1
H NMR spectrum of unsaturated [C
4
EO
5
π
]
n
polymer in CDCl
3
.
Figure 14.
13
C NMR spectrum of unsaturated [C
4
EO
5
π
]
n
polymer in CDCl
3
.
21
1.5.8 NMR Spectra of [C
4
EO
5
]
n
1
H NMR spectrum in ppm (CDCl
3
, 400 MHz): 3.68B3.53 (m, 4H); 3.44 (t,
J
= 6.8 Hz, 4H);
1.65B1.50 (m, 2H); 1.42B1.25 (m, 2H); 0.91 (t,
J
= 7.4 Hz, endgroup).
13
C NMR spectrum in ppm
(CDCl
3
, 125 MHz): δ 71.57, 70.75, 70.72, 70.19, 29.74, 26
.12.
Figure 15.
1
H NMR of [C
4
EO
5
]
n
polymer in CDCl
3
.
Figure 16.
13
C NMR spectrum of [C
4
EO
5
]
n
polymer in CDCl
3
.
22
1.5.9 NMR Spectra of Unsaturated [C
6
EO
4
π
]
n
1
H NMR spectrum in ppm (CDCl
3
,
400 MHz): δ 5.87B5.75 (m, endgroup); 5.46B5.37 (m,
trans
alkene, 2H when combined with
cis
Balkene); 5.36 (t,
J
= 4.6 Hz,
cis
Balkene); 5.06B4.90 (m, endgroup);
3.69B3.51 (m, 12H); 3.44 (td,
J
= 6.7, 2.1 Hz, 4H); 2.21B1.92 (m, 4H); 1.70B1.56 (
m, 4H).
13
C NMR
spectrum in ppm (CDCl
3
, 125 MHz): δ 130.14, 129.72, 70.97, 70.74, 70.24,
70.22, 29.70, 29.58, 29.16,
23.82.
Figure 17.
1
H NMR of unsaturated [C
6
EO
4
π
]
n
polymer in CDCl
3
.
Figure 18.
13
C NMR spectrum of unsaturated [C
6
EO
4
π
]
n
polymer in CDCl
3
.
23
1.5.10 NMR Spectra of [C
6
EO
4
]
n
13
H NMR spectrum in ppm (CDCl
3
, 400 MHz): 3.69B3.53 (m, 12H); 3.43 (t,
J
= 6.8 Hz, 4H);
1.80 (br s, endgroup); 1.62B1.49 (m, 4H); 1.28 (br
s, 8H); 0.88 (br s, endgroup).
13
C NMR spectrum in
ppm (CDCl
3
, 125 MHz): δ 71.65, 70.75, 70.73, 70.18, 29.76, 29
.58, 26.18.
Figure 19.
1
H NMR spectrum of [C
6
EO
4
]
n
polymer in CDCl
3
.
Figure 20.
13
C NMR spectrum of [C
6
EO
4
]
n
polymer in CDCl
3
.