Macromolecules
Article
1
3
1
organic phase was dried over MgSO and vacuum filtered, and the
(m, 1H), 6.35 (s, 2H), 4.17−4.25 (m, 8H). C{ H} NMR (500
4
filtrate was evaporated. The residue was further purified via column
chromatography. The first fraction (impurities) was collected by
CH Cl ; afterward, the second fraction (product) was collected via
MHz, δ ppm, CD CN, 298 K): 207.4, 160.4, 158.4, 154.5, 153.9,
3
151.4, 143.1, 142.8, 140.3, 139.0, 137.6, 136.9, 127.3, 127.2, 126.6,
124.1, 123.8, 119.8, 108.2, 106.0, 99.0, 65.96, 65.58. Elemental
analysis calculated for C H ClF N O PRuS : C, 42.65; H, 2.71; N,
2
2
ethyl acetate. The product was redissolved in CH Cl with hexanes
2
2
33 25
6
7
4
2
added to remove tributylstannyl impurities. The tan precipitate was
10.55; found: C, 42.11; H, 2.77; N, 10.62. MS (ESI) calculated for
1
+
collected as 0.355 g (48% yield). H NMR (400 MHz, δ ppm, CDCl ,
C H ClN O RuS m/z = 784.01 ([M − PF ] ); found 784. UV−vis
3
33 25
7
4
2
6
3
2
98 K): 8.72 (s, 2H), 8.00 (s, 2H), 7.92−7.97 (dd, 1H, J = 7.95
(CH Cl , nm (ε)): 254 (30553), 290 (66486), 355 (21887), 455
H,H
2 2
3
Hz, 1.80 Hz), 7.82−7.84 (d, 2H, J = 7.9 Hz), 6.25 (s, 2H), 4.36
(8894), 550 (4119).
H,H
1
3
1
(
m, 4H), 4.24 (m, 4H). C{ H} NMR (100 MHz, δ ppm, CDCl ,
[Ru(L)(phen)(Cl)](PF ) (8). 4 (50 mg, 0.0713 mmol) and 1,10-
3
6
2
1
4
98 K): δ = 149.9, 141.9, 141.2, 140.1, 137.8, 122.8, 116.8, 109.4,
phenanthroline (phen) (14.5 mg, 0.08 mmol) were refluxed for 12 h
08.3, 96.4, 64.9, 64.6. MS (ESI) calculated for C H N O S m/z =
in 30 mL of EtOH/H O (3/1, v/v) under N . The reaction mixture
2
3
18
5
4
2
2
2
+
92.08 ([M + H] ); found 492.12. UV−vis (CH Cl , nm (ε)): 277
was filtered through Celite as hot. NH PF (1g/10 mL) was added
2
2
4 6
(
21969), 315 (24507) sh, 335 (29034).
Ru(L)Cl (4). RuCl ·XH O (167 mg, 0.805 mmol) and 3 (202 mg,
into filtrate and stirred for 1 h. The solvent was evaporated. The
residue was redissolved in CH Cl and then washed with H O once.
3
3
2
2
2
2
0
.411 mmol) were heated to reflux in ethanol (60 mL) for 12 h. After
The organic phase was dried over MgSO and vacuum filtered; the
4
cooling, the precipitate was collected by filtration, washed with
ethanol, and then dried under high vacuum to give a black insoluble
solid (250 mg, 81.4%).
filtrate was evaporated and further dried under vacuum to afford a
reddish-brown solid (39 mg, 58%). H NMR (400 MHz, δ ppm,
1
CD CN, 298 K): 10.43 (dd, 1H), 8.90 (s, 2H), 8.78 (dd,1H), 8.23−
3
Ru(L)(hfac)(Cl) (5). A mixture of 4 (101 mg, 0.144 mmol),
triethylamine (0.81 mL, 5.81 mmol), and 1,1,1,5,5,5-hexafluoro-2,4-
pentanedione (hfac) (0.60 mL, 4.24 mmol) in 100 mL of absolute
ethanol was heated at reflux under Ar for 12 h. The reaction mixture
was allowed to cool, and the solvent was removed by rotary
evaporation. The solid residue was redissolved in CH Cl and filtered
8.29 (m, 4H), 8.04−8.08 (m, 3H), 7.74 (dd, 1H), 7.34 (s, 2H), 7.30
1
3
1
(dd, 1H), 6.28 (s, 2H), 4.11−4.19 (m, 8H). C{ H} NMR (500
MHz, δ ppm, CD CN, 298 K): 207.4, 155.2, 154.4, 151.7, 150.8,
3
149.8, 143.1, 140.2, 139.0, 136.5, 135.8, 131.7, 131.0, 128.7, 128.1,
127.3, 126.4, 125.3, 119.7, 108.2, 105.9, 98.9, 65.89, 65.54. MS (ESI)
+
calculated for C H ClN O RuS m/z ([M − PF ] ) = 808.01;
2
2
35 25
7
4
2
6
to remove insolubles. The filtrate was adsorbed on alumina to run a
found 808. UV−vis (CH CN, nm (ε)): 223 (53267), 265 (66997),
3
column chromatography with 0.5% CH OH in CH Cl as the eluent.
349 (18970), 443 (11820), 549 (4033).
3
2
2
The second fraction was the product, but there were still
triethylamine impurities. The product was then extracted between
CH Cl and H O. The organic phase was dried over MgSO and
X-ray Crystallography. Data were collected on a Rigaku
MiniFlex II CCD diffractometer with graphite monochromated Mo
Kα radiation (λ = 0.71073 Å) at 223 K. The data set was corrected for
absorption based on multiple scans and reduced using standard
methods. The structures were solved by direct methods and refined
anisotropically using full-matrix least-squares methods with the
2
2
2
4
vacuum filtered; the filtrate was evaporated and further dried under
1
vacuum (81 mg, 67%). H NMR (400 MHz, δ ppm, CD Cl , 298 K):
2
2
8
.63 (s, 2H), 8.24 (s, 2H), 7.64 (t, 1H, J = 8.4 Hz), 7.47 (d, 2H, J = 8
1
9
40
Hz,), 6.34 (s, 2H), 6.10 (s, 1H), 4.26−4.34 (m, 8H). F NMR (376
SHELX 97 program package. Coordinates of the non-hydrogen
MHz, δ ppm, CD Cl , 298 K): δ = −75.11, −75.62. MS (ESI)
atoms were refined anisotropically, while hydrogen atoms were
included in the calculation isotropically but not refined. Neutral atom
2
2
+
calculated for C H ClF N O RuS : m/z = 835.94 ([M + H] ),
2
8
18
6
5
6
2
+
+
+
41
7
99.96 ([M − Cl] ); found 836 ([M + H] ), 799 ([M − Cl] ). UV−
scattering factors were taken from Cromer and Waber.
vis (CH Cl , nm (ε)): 281 (29011), 316 (21986) sh, 354 (12247),
Electrochemistry/Electropolymerization. The GPES system
from Eco. Chemie was used to carry out electrochemistry and
electropolymerization experiments in the glovebox with three
2
2
4
97 (6896). A solution of 5 in chloroform was slowly evaporated to
obtain X-ray quality crystals.
Ru(L)(dbm)(Cl) (6). A mixture of 4 (127 mg, 0.182 mmol),
triethylamine (0.95 mL, 6.82 mmol), and dibenzoylmethane (dbm)
electrodes, i.e., Ag/AgNO as the reference electrode, a Pt wire coil
3
as the counter electrode, and a Pt button as the working electrode.
For the UV−vis and luminescence measurements of the polymers,
Delta Technologies ITO-coated glass was used as a working electrode
instead of the Pt button. The reference electrode consists of a Ag wire
which was in a 0.01 M AgNO solution with 0.1 M [(n-Bu) N][PF ]
(
55.3 mg, 0.254 mmol) in 127 mL of absolute ethanol was heated to
reflux under Ar for 12 h. The reaction mixture was allowed to cool,
and the solvent was removed by rotary evaporation. The solid residue
was redissolved in CH Cl and filtered to remove insolubles. The
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2
3
4
6
filtrate was washed with NH Cl solution once, then dried over
(TBAPF ) in CH CN. Potentials measured were relative to the
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6 3
MgSO , and vacuum filtered. Hexanes was added into the filtrate to
reference electrode which needed to be calibrated by external
reference ferrocene. Calibrations were performed before and after
experiments were performed. The average of the ferrocene measure-
ments was determined and used to correct the measured potentials.
Solution of 0.1 M (TBAPF ) in CH Cl was used as the electrolyte.
4
precipitate the product which was collected via vacuum filtration. The
dark burgundy product was further dried under vacuum (97 mg,
1
6
8
7
3%). H NMR (400 MHz, δ ppm, CD Cl , 298 K): 8.66 (s, 2H),
2
2
.34 (m, 2H), 8.11 (s, 2H), 7.51−7.62 (6H), 7.17−7.14 (m, 3H),
6
2
2
−
3
.06 (t, J = 8 Hz, 2H), 6.64 (s, 1H), 6.26 (s, 2H), 4.19−4.29 (m, 8H).
∼1 × 10 M monomer solutions were prepared for electro-
polymerizations. The potential windows were between ∼−1.6 and
MS (ESI) calculated for C H ClN O RuS m/z = 852.03 ([M +
3
8
28
5
6
2
+
+
+
+
−1
H] ), 816.05 ([M − Cl] ); found 852 ([M + H] ), 815 ([M − Cl] ).
UV−vis (CH Cl , nm (ε)): 256 (35714), 279 (38713), 326 (52803),
86 (8153). A solution of 6 in chloroform was slowly evaporated to
∼1.25 V at the scan rate of 100 mV s . The polymer films were
washed with dry CH Cl in the glovebox to remove any monomer or
2
2
2
2
4
electrolyte left on the films before further experiments. TBAPF had
6
to be purified. Hot ethanol was used to recrystallize TBAPF three
times, and then the white crystals were dried for 3 days above 100 °C
under active vacuum.
6
mL of EtOH/H O (3/1, v/v). The hot solution was filtered through
Luminescence Studies. Optical density of all complexes was
about 0.1 absorbance unit to exclude any excimer formation and
concentration quenching effect. After having a proper range of optical
density (0.05−0.1 A), fresh stock solutions were transferred into
capped and parafilmed quartz EPR (electron paramagnetic resonance)
tubes as well as airtight quartz cuvettes in the glovebox. Measure-
ments with airtight cuvettes could only be performed at RT (no dewar
available), but samples in EPR tubes were suitable for both RT and 77
K measurements. Dry solvents of 2-MeTHF, EtOH, and MeOH were
degassed by freeze−pump−thaw technique for 4−5 cycles and then
2
Celite and evaporated to dryness. After dissolving the crude product
in CH Cl , 26 mg of KPF was added; the mixture was stirred
2
2
6
overnight. The resulting brown precipitate was collected via vacuum
filtration. The product was redissolved in CH Cl , and pentane was
2
2
1
layered. The solid was collected a week later (60 mg, 45%). H NMR
400 MHz, δ ppm, CD CN, 298 K): 10.25 (m, 1H), 8.92 (s, 2H),
(
3
8
1
7
.56 (d, J = 8.0 Hz, 1H), 8.32 (d, J = 7.6 Hz, 1H), 8.23−8.27 (m,
H), 8.18−8.22 (m, 1H), 8.01 (d, J = 8 Hz, 2H), 7.89−7.92 (m, 1H),
.70−7.74 (m, 1H), 7.5 (s, 2H), 7.38 (d, J = 8.0 Hz, 1H), 6.96−7.00
C
Macromolecules XXXX, XXX, XXX−XXX