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 )

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Luminance (cd/m

2)

0 5 10 15 20 250.00

0.01

0.02

0.03

0.04

0.05

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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

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0.25

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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

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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.

Fig. S18 1H-NMR spectrum of compound 1.

Fig. S19 13C-NMR spectrum of compound 1.

Fig. S20 1H-NMR spectrum of Compound 2.

Fig. S21 13C-NMR spectrum of Compound 2.