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TRANSCRIPT
Packing Directed Beneficial Role of 3-D Rigid Alicyclic
Arms on Templated Molecular Aggregation Problem
Sunil Kumar,a Punita Singh,b Ritu Srivastava, Subrata Ghosha,*
aSchool of Basic Sciences, Indian Institute of Technology Mandi, Mandi-175001, H.P, India
bPhysics of Energy Harvesting Division, National Physical Laboratory, New Delhi, India
Synthesis.
O
O
CN
HO
O
O
CN
RCOCl, TEA
rt, 6hrsO
(2) R =
O
R
(1) R =
Scheme S1. Synthesis pathway to compound 1 and compound 2.
Compound 1. To a dichloromethane suspension of hydroxyl coumarin (1eq) was added
triethylamine (2.5 eq) followed by the addition of 1-adamantanecarbonyl chloride (1eq) at 0°C
and reaction mixture was then stirred at room temperature for 6 hours. Progress of reaction was
checked using thin layer chromatography (TLC). Reaction mixture was extracted with
dichloromethane and washed with water (30ml x 3). Organic layer was dried over sodium sulfate
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015
and concentrated over high vacuum. Light green compound was obtained as product after hexane
washings.
1H-NMR: δ/ppm (500 MHz, CDCl3) = 8.57 (d, J = 9.6 Hz, 1H), 7.58 – 7.51 (m, 5H), 7.48 – 7.42
(m, 2H), 7.39 – 7.34 (m, 1H), 7.25 (d, J = 8.2 Hz, 1H). 2.05 – 2.03 (m, 10H), 1.72 – 1.69 (m 5H).
13C-NMR: δ/ppm (125 MHz, CDCl3) =175.8, 164.7, 157.2, 152.8, 137.2, 132.1, 131.08, 129.2,
128.4, 125.1, 124.7, 123.6, 123.4, 120.4, 119, 113.7, 113.3, 100.5, 41.3, 38.7, 36.3, 27.8. IR: υ
max/cm-1 = 3020, 2955, 2228, 1724, 1634, 1584, 1533, 1501, 1391.2, 1343, 1273, 1229, 1151,
1030, 880, 754. HRMS: m/z calculated for C31H25NO4 : Exact Mass: 475.1784 , found [MH]+ =
476. 1857; M.P. = 297°C; Yield = 69%.
Compound 2. To a tetrahydrofuran suspension of hydroxyl coumarin (1eq) was added
triethylamine (2.5 eq) followed by the addition of 2-(bicyclo[2.2.1]heptan-2-yl)acetyl chloride
(1.1eq) at 0°C and reaction mixture was then stirred at room temperature for 6 hours. Progress of
reaction was checked using thin layer chromatography (TLC). Reaction mixture was extracted
with ethyl acetate and washed with water (30ml x 3). Organic layer was dried over sodium
sulfate and concentrated over high vacuum. Light green compound was obtained as product.
1H-NMR: δ/ppm (500 MHz, CDCl3) = 8.63 (d, J = 9.6 Hz, 1H), 7.65 – 7.60 (m, 5H), 7.53 – 7.51
(m, 2H), 7.46 – 7.44 (m, 1H), 7.32 (d, J = 8.9 Hz, 1H). 2.63 – 2.59 (m, 1H), 2.48 – 2.43 (m, 1 H),
2.30 (bs, 1H), 2.13 – 2.12 (m, 1H), 2.08 – 2.05 (m, 1H), 1.63 – 1.51 (m, 4H), 1.40 – 1.38 (m,
1H), 1.31 – 1.25 (m, 1H), 1.21 – 1.19 (m, 3H). 13C-NMR: δ/ppm (125 MHz, CDCl3) =171.1,
164.6, 157.1, 152.3, 137.2, 132.1, 131.0, 129.2, 128.4, 125.1, 124.8, 123.6, 123.3, 120.5, 118.9,
113.7, 113.3, 100.5, 41.26, 41.22, 38.4, 37.7, 36.7, 35.2, 29.7, 28.4. IR: υ max/cm-1 = 3120,
2950, 2234, 1730, 1620, 1581.5, 1542.6, 1511, 1391, 1349, 1273, 1229, 1166, 1020.8, 873, 746.
HRMS: m/z calculated for C29H23NO4 Exact Mass: 449.1627, found [MH]+ = 450.1699,
[M+Na]+ = 472.1521. M.P. = 210°C; Yield = 65%.
Synthesis of 2-(bicyclo[2.2.1]heptan-2-yl)acetyl chloride.
2-Norbornaneacetic acid (1eq) was dissolved in dry tetrahydrofuran and one drop of
dimethylformamide was added. Thionyl chloride (SOCl2, 2eq) was added dropwise at 0°C.
Reaction mixture was then refluxed for 3 hours. Reaction mixture was then concentrated over
vacuum to remove unreacted SOCl2 and kept under nitrogen. The yellow liquid obtained was
used immediately without any purification.
Table S1. Crystal data and structure refinement for compound 2.
Compound 2Empirical formula C29H23NO4Formula weight 449.48Crystal System MonoclinicSpace group P21/ca/Å 31.1736(9)b/Å 9.5651(2)c/Å 8.0016(3)α,β, γ, deg 90, 91.296(3), 90.00Volume/Å3 2385.28(12)Z, ρcalcmg/mm3, μ/mm-1 4, 1.252, 0.673Crystal size/mm3 0.3017 × 0.087 × 0.0558 2Θ range for data collection 8.52 to 133.54° Index ranges -36 ≤ h ≤ 37, -11 ≤ k ≤ 3, -9 ≤ l ≤ 9 Reflections collected 7164 Independent reflections 4175[R(int) = 0.0187] Data/restraints/parameters 4175/0/307 Goodness-of-fit on F2 1.050 Final R indexes [I>=2σ (I)] R1 = 0.0659, wR2 = 0.1911 Final R indexes [all data] R1 = 0.0783, wR2 = 0.2066 Largest diff. peak/hole / e Å-3 0.39/-0.26
350 400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0No
rmal
ized
inte
nsity
(a.u
)
Wavelength (nm)
DCM THF DMF DMSO
(a)
400 450 500 5500.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d In
tens
ity (a
.u)
Wavelength (nm)
DCM THF DMF DMSO
(b)
Fig. S1 Photoluminescence solvatochromism spectra for (a) compound 1 and (b) 2.
300 400 500 6000.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d ab
sorp
tion
(a.u
)
Wavelength (nm)
hydroxy coumarin 1 2
(a)
300 400 500 600 700
0.0
0.2
0.4
0.6
0.8
1.0No
rmal
ised
abso
rptio
n(a.
u)
Wavelength (nm)
Compound 1 DCM THF DMF DMSO
(b)
300 400 500 600 700
0.0
0.2
0.4
0.6
0.8
1.0
Norm
aliz
ed ab
sorp
tion
(a.u
)
Wavelength (nm)
Compound 2 DCM THF DMF DMSO
(c)
Fig. S2 (a) Comparison of UV-vis absorption spectra of 1 and 2 with parent hydroxyl coumarin; (b) UV-vis absorption solvatochromism spectra for 1 and (c) UV-vis absorption solvatochromism spectra for 2.
400 450 500 5500
50
100
150
200
250
300
350
400
Norm
alize
d In
tens
ity (a
.u)
Wavelength (nm)
water content 0% 20% 40% 50% 60% 80% 90%
420 440 460 480 500 520 540 5600
100
200
300
400
500
600
Nor
mal
ized
Inte
nsity
(a.u
)
Wavelength (nm)
water content 0% 20% 40% 50% 60% 80% 90%
Fig. S3. PL changes in THF:water experiment with increasing water content for compounds 1 (a) and 2 (b).
Fig. S4 Interplanar angle between 2H-benzo[h]chromen-2-one core and phenyl moiety of compound 2.
-1.6 -1.2 -0.8 -0.4 0.0
Nor
mal
ized
curre
nt (a
.u)
Voltage (V)
Compound 1(a)
-1.2 -0.8 -0.4 0.0
Nor
mal
ized
curre
nt (a
.u)
Voltage (V)
Compound 2(b)
(a) (b)
Fig. S5 Cyclic voltammetry curves showing reduction potential window for compound 1 and 2. (ELUMO = -[(Ered + 4.8)] eV, where Ered is the onset reduction potential relative to the (Fc/Fc+) couple. E1/2 (Fc/Fc+) = 0.58 eV (DCM) and 0.55 (ACN). EHOMO = ELUMO + Eg).
Fig. S6 Optimized geometry of compound 1 calculated at B3LYP/6-311G (d,p) level of DFT.
Fig. S7 Optimized geometry of compound 2 calculated at B3LYP/6-311G (d,p) level of DFT.
Compound 2
Wavelength, nm 390 380 370 360 350 340 330 320 310 300 290 280
f
0.4 0.38 0.36 0.34 0.32 0.3
0.28 0.26 0.24 0.22 0.2
0.18 0.16 0.14 0.12 0.1
0.08 0.06 0.04 0.02
0
LUMO+1 = 1.77 eV
HOMO = 6.45 eV LUMO = 2.77 eV
HOMO LUMO
HOMO LUMO+1
Fig. S8 TD-DFT absorption spectra of compound 1 calculated atB3LYP/6-311G(d,p) level. Peaks are characterized with their major electronic transition. Orbitals involved in electronic transitions are also depicted.
compound 3
Wavelength, nm 390 380 370 360 350 340 330 320 310 300 290 280
f
0.4 0.38 0.36 0.34 0.32 0.3
0.28 0.26 0.24 0.22 0.2
0.18 0.16 0.14 0.12 0.1
0.08 0.06 0.04 0.02
0
HOMO = -6.45 eV LUMO = 2.80 eV
LUMO+ 1 = 1.79 eV
HOMO LUMO
HOMO LUMO+1
Fig. S9 TD-DFT absorption spectra of compound 2 calculated atB3LYP/6-311G(d,p) level. Peaks are characterized with their major electronic transition. Orbitals involved in electronic transitions are also depicted.
0 2 4 6 8 10 12 14 16 18 200.000
0.002
0.004
0.006
0.008
Device 1
Voltage (V)
Cur
rent
eff
icie
ncy
(cd/
A)
0.0000
0.0005
0.0010
0.0015
0.0020
0.0025
Power efficiency (Lm
/W)
0 2 4 6 8 10 12 14 16 18 200
200
400
600
800
1000 Device 1
Voltage (V)
Cur
rent
den
sity
(mA
/cm
2 )
0
10
20
30
40
Luminance (cd/m
2)
Fig. S10 J–V–L characteristics (left) and Current efficiency–voltage and power efficiency–voltage (right) of Device 1.
0 5 10 15 20 25
0
200
400
600
800
1000 Device 2
Voltage (V)
Cur
rent
den
sity
(mA
/cm
2 )
0
10
20
30
40
50
60
Luminance (cd/m
2)
0 5 10 15 20 250.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07 Device 2
Voltage (V)
Cur
rent
eff
icie
ncy
(cd/
A)
0.000
0.005
0.010
0.015
0.020
0.025
Power efficiency (Lm
/W)
Fig. S11 J–V–L characteristics (left) and Current efficiency–voltage and power efficiency–voltage (right) of Device 2.
0 2 4 6 8 10 12 14 16 18 200.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
Device 3
Voltage (V)
Cur
rent
eff
icie
ncy
(cd/
A)
0.00
0.06
0.12
0.18
Power efficiency (Lm
/W)
0 2 4 6 8 10 12 14 16 18 200
200
400
600
800
1000
1200
1400
Device 3
Voltage (V)
Cur
rent
den
sity
(mA
/cm
2 )
0
20
40
60
80
100
120
140
160
Luminance (cd/m
2) Fig. S12 J–V–L characteristics (left) and Current efficiency–voltage and power efficiency–voltage (right) of Device 3.
0 5 10 15 20
0.00
0.01
0.02
0.03
0.04
0.05
0.06 Device 4
Voltage (V)
Cur
rent
eff
icie
ncie
(cd/
A)
-0.002
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0.018
0.020
Pow
er efficiency (Lm/W
)
0 5 10 15 200
200
400
600
800 Device 4
Voltage (V)
Cur
rent
den
sity
(mA
/cm
2 )
0
10
20
30
40
50
60
Luminance (cd/m
2)
Fig. S13 J–V–L characteristics (left) and Current efficiency–voltage and power efficiency–voltage (right) of Device 4.
0 5 10 15 20
0.00
0.06
0.12
0.18 Device 5
Voltage (V)
Curr
ent e
ffic
ienc
y (c
d/A
)
0.00
0.02
0.04
0.06
0.08
0.10
Power efficiency (Lm
/W)
0 5 10 15 20
0
200
400
600
800
1000
1200
1400
Device 5
Voltage (V)
Cur
rent
den
sity
(mA
/cm
2 )
0
20
40
60
80
100
Luminance (cd/m
2)Fig. S14 J–V–L characteristics (left) and Current efficiency–voltage and power efficiency–voltage (right) of Device 5.
200 400 600 800 1000 12000.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d In
tensit
y(a.u
)
Wavelength (nm)
Device 3 13V 14V 15V
Fig. S15 Electroluminescence spectrum of Device 3 at 13V, 14V and 15V.
400 500 600 700 8000.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d In
tensit
y (a
.u)
Wavelength (nm)
Device 5 (19V)
Fig. S16 Electroluminescence spectrum of Device 5 at 19V.
400 600 8000.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d In
tensit
y (a
.u)
Wavelength (nm)
24V
Fig. S17 Electroluminescence spectrum of Device 6 at 24V.