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Supporting Information
Tuning of multiple luminescence output and white-light emission from a single gelator molecule through ESIPT coupled AIEE process
Arunava Maity,a Firoj Ali,a Hridesh Agarawal,a Bihag Anothumakkoolb and
Amitava Dasa
aOrganic Chemistry Division, bPhysical & Materials Chemistry Division, CSIR-
National Chemical Laboratory, Pune-411008, Maharashtra, India; E-mail:
[email protected]; Fax: +91 2025902629; Tel: +91 2025902385.
Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2014
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Table of contents: Page No
Materials and methods S3
General description of different experimental techniques S4
Synthetic scheme S5
Synthesis and characterization of [4] S6
Synthesis and characterization of [1] and [2] S6
References S7
1H NMR spectra of [4] S8
13C NMR spectra of [4] S9
Mass spectra of [4] S10
1H NMR spectra of [1] S11
13C NMR spectra of [1] S12
Mass spectra of [1] S13
1H NMR spectra of [2] S14
13C NMR spectra of [2] S15
Mass spectra of [2] S16
UV-Vis absorption spectra of [1] S17
Variable-temperature UV-Vis absorption spectra of [1] S17
Weight-loss profile (TGA plot) of [1] S18
Comparisons between absorption and excitation spectra of [1] S18
UV-Vis absorption spectra of [2] S20
Solvent dependent emission spectra of [2] S21
Emission spectra of [1] in different polarities of solvents S21
Comparisons of FT-IR spectrum between compound [1] and [2] S22
Gelation study of [2] S23
Photographs showing the changes of emission color of [1] S23
Schematic route for gelation of [1] S24
Rheological property of [1] S25
XRPD pattern of [1] S25
I-V characteristic plot of [1] S26
Solvent dependent FESEM images of [1] S26
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Materials and methods:
Unless otherwise stated, all reagents used for synthesis purpose were purchased from
commercial suppliers, and used as such without further purification. Organic solvents were
purified according to the standard procedure.1 HPLC grade solvents were used for recording
spectrometric data. FTIR spectra were recorded as KBr pellets in a cell fitted with a KBr
window, using a Perkin-Elmer Spectra GX 2000 spectrometer. 1H and
13C NMR spectra have
been recorded on a Bruker 200/400/500 MHz FT NMR (Model: Avance-DPX 200/500) and all
spectra were calibrated against TMS. Mass spectrometric data were acquired by an electron
spray ionization (ESI) technique on a Q-tof-micro quadruple mass spectrometer (Micro mass).
High-resolution mass spectra were recorded on JEOL JM AX 505 HA mass spectrometer.
Thermo-gravimetric analyses (TGA) were carried out on a TG50 analyzer (Mettler-Toledo) or a
SDT Q600 TG-DTA analyzer under a N2 atmosphere at a heating rate of 10°C min
-1 within a
temperature range of 20–800 oC. UV-Vis spectra were recorded using a PerkinElmer Lambda-
950 UV-Vis spectrometer equipped with a peltier system for variable temperature experiments,
while fluorescence as well as fluorescence excitation spectra were recorded using Qunata Master
400, PTI spectrofluorometer. FESEM images were obtained using Nova Nano SEM 450 and
Quanta™ Scanning Electron Microscope. TEM images were recorded using a FEI Tecnai G2
F20 X-TWIN TEM at an accelerating voltage of 200 kV. Rheology was performed using a TA-
ARES rheometer equipped with a force rebalance transducer. X-ray powder diffraction (XRPD)
of air dried THF gel of 1 were recorded on a Phillips PANalytical diffractometer for Cu Kα
radiation (λ = 1.5406 Å).
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General description of different experimental techniques:
UV-Vis and Fluorescence spectrum measurements: Stock solutions of both compounds (1 and
2) were made in THF (1.0 μM). An aliquot (0.5 mL) was taken and was added with an
appropriate amount of THF and water (H2O) to adjust the desired solvent composition and final
concentration (10 µM). Each solution was allowed to equilibrate at room temperature for 1h
before spectral measurements. For variable-temperature experiments compound-1 solution in
THF/Water (3:7) was heated from lowest to highest temperature and allowed to equilibrate for
15 min at the desired temperature before each measurement. All luminescence measurements
were recorded using, λExt = 365 nm and 306 nm for compound 1 and 2 respectively with an
emission slit width of 2 nm. Fluorescence excitation spectra were recorded using the same
solution used for fluorescence studies.
General procedure for gelation study: Due to the limited solubility of 1 in common organic
solvent, gelation property of 1 was checked with three specified solvents, namely DMF, DMSO
and THF. Compound 1 was highly soluble in DMF and DMSO, which were not suitable for
studying the gelation phenomena. Whereas in case of THF solvent, A weighted amount 1 was
dissolved in THF (1.0 mL) by heating in closed vials. The clear solution was left to cool down in
air at 25oC without any disturbance. The gel formation was confirmed by the failure of the soft
mass to flow by inverting the glass vial.
Scanning electron microscopy (SEM): A solution of 1 (100 μM) in THF as well as in different
composition of THF/water mixture were drop-casted on silicon wafer and allowed to air dry for
6-7 hrs in a dust free place. Finally it was dried under desiccator for overnight. Before taking
images samples were coated with gold vapor.
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Transmission Electron Microscopy (TEM): TEM samples were prepared drop-casting the 1.0
mM THF solution of 1 onto carbon coated copper grids (200 mesh). TEM images were obtained
after drying the sample in vacuum for 24 hours.
Current (I) - voltage (V) measurements: The gel solution of 1 (10.0 mg/mL of THF) was drop-
casted on indium tin oxide (ITO) coated glass surfaces and dried for 24 hrs at room temperature.
I-V characteristic profile of this sample was measured in a two-probe electrode using a
KEITHLEY 4200-SCS programmable electrometer instrument.
Synthetic scheme:
Sceme-1: Methodologies that were adopted for synthesis of [1], [2], [3a & 3b], [4] and [5].
S6
Synthesis of [3a & 3b]: 3a and 3b were synthesized following the previously reported
procedure.2
Synthesis and characterization of [4]: In a 100 mL two neck RB 3,5-bisformyl-4-hydroxy
ethyl benzoate [3b]2 (200.0 mg, 0.9 mMol), commercially available benzyl bromide (169.5 mg,
0.99 mMol) , anhydrous K2CO3 were mixed in 20~25 mL dry acetonitrile (ACN) . Followed by a
pinch of tertiary butyl ammonium iodide (tBu)NH4+I- was added and was reflux for 24 h under
N2 atmosphere. The reaction mixture was cooled to room temperature; solvent was then removed
under reduced pressure using a rotary evaporator. Oily residue was taken in 80 mL of CHCl3,
and washed with distilled water (3 X 30 mL). Organic layer dried over anhydrous Na2SO4.
Finally solvent was evaporated to get crude product as a color less oil. It was purified by column
chromatography using silica gel as stationary phase and 25% ethyl acetate in hexane as eluent to
obtain pure product as white solid. Yield = 35%, 1H NMR (CDCl3, 200 MHz, TMS): δ (ppm) =
10.23 (2H, s, -CHO); 8.72 (2H, s, ArH); 7.41-7.36 (3H, m, ArH); 7.32-7.29 (2H, m, ArH); 5.24
(2H, s, -CH2); 4.47-4.36 (2H, q, J = 7Hz, -CH2 ester); 1.44-1.37 (3H, t, J = 7.2Hz, -CH3 ester);
13C NMR (CDCl3, 400 MHz, TMS): δ (ppm) = 14.72, 59.51, 61.84, 81.71, 127.52, 128.98,
129.06, 129.56, 130.57, 134.02, 138.35, 164.35, 165.81, 187.82; HRMS (ESI): m/z calculated
for C18H16O5Na [M + Na]+: 335.0890; found 335.0884.
Synthesis of [5]: Compound [5] was synthesized according to the previously reported
procedure.3
Synthesis and characterization of [1] and [2]: Synthetic procedure of both compounds was
followed according to reported procedure3 with slide modification
. A solution of compound [3a]
(136.2 mg, 0.7 mMol) or [4] (219.1 mg, 0.7 mMol) in methanol was added drop wise to a CHCl3
solution of compound [5] (638.0 mg, 1.4 mMol). The reaction mixture was stirred at room
S7
temperature for 9~10 hour, resulting precipitate [for compound-1 (yellow) and for compound-2
(color less)] was filtered off using G4-gooch crucible. Washed with (1:1) CHCl3/MeOH mixture
several times, dried under desiccator to obtain the pure product.
[1]: Yield = 90%; 1H NMR (DMSO-d6, 500 MHz, TMS): δ (ppm) = 13.30 (1H, s, -COOH);
12.18 (2H, s, -NH); 8.82 (2H, s, -CH=N); 8.34 (2H, s, ArH); 7.51-7.49 (8H, d, J = 7Hz, ArH);
7.45-7.40 (12H, m, ArH); 7.37-7.36 (8H, m, ArH), 7.28-7.27 (6H, m, ArH); 5.22 (8H, s,
ArCH2O); 5.04 (4H, s, ArCH2O); 13
C NMR (DMSO-d6, 400 MHz, TMS): δ (ppm) = 70.44,
74.22, 106.95, 120.23, 122.18, 127.65, 127.82, 127.91, 128.01, 128.11, 128.39, 130.84, 136.67,
137.30, 140.30, 145.15, 152.08, 159.82, 162.27, 166.37; HRMS (ESI): m/z calculated for
C65H55O11 N4 [M + H]+: 1067.3862; found 1067.3861.
[2]: Yield = (84%); 1H NMR (DMSO-d6, 400 MHz, TMS): δ (ppm) = 11.94 (2H, s, -NH); 8.75
(2H, s, -CH=N); 8.57 (2H, s, ArH); 7.56-7.54 (2H, m, ArH); 7.50-7.48 (6H, m, ArCH2O);7.43-
7.34 (26H, m, ArH); 7.29-7.27 (5H, m, ArH); 5.22 (8H, s, ArCH2O); 5.04 (6H, s, ArCH2O);
4.42-4.41 (2H, board, -CH2 ester); 1.37 (3H, board, -CH3 ester); 13
C NMR (DMSO-d6, 500 MHz,
TMS): δ (ppm) = 14.22, 61.22, 70.48, 74.25, 78.44, 107.05, 126.56, 127.56, 127.87, 127.94,
128.05, 128.15, 128.34, 128.41, 128.58, 128.92, 129.20, 135.29, 136.71, 137.31, 140.25, 141.57,
152.07, 159.11, 162.80, 164.77; HRMS (ESI): m/z calculated for C74H65O11N4 [M + H]+:
1185.4644; found 1185.4647.
References:
1. Perrin, D. D.; Armarego, W. L. F. Perrin, D. R. Purification of Laboratory Chemicals,
2nd ed., Pergamon, Oxford, 1980
2. Naama Karton-Lifshin, Lorenzo Albertazzi, Michael Bendikov, Phil S. Baran and Doron
Shabat, J. Am. Chem. Soc., 2012, 134, 20412.
3. P. Rajamalli and E. Prasad, Org. Lett., 2011. 13, 3714.
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1H NMR spectra of [4]:
SI Fig.S1: 1H NMR spectra of [4] in CDCl3 recorded in 200 MHz.
S9
13C NMR spectra of [4]:
SI Fig.S2: 13
C NMR spectra of [4] in CDCl3 recorded in 400 MHz.
S10
Mass spectra of [4]:
AMB2-36 #911 RT: 4.06 AV: 1 NL: 7.64E7
T: FTMS + p ESI Full ms [60.00-900.00]
260 270 280 290 300 310 320 330 340 350 360
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lativ
e A
bu
nd
an
ce
335.0884
R=61807
C18 H16 O5 Na = 335.0890
-1.8379 ppm
288.9214
R=66102
301.1404
R=64402 350.8919
R=60102282.9045
R=65702264.9540
R=67402327.1221
R=60807
343.0694
R=59307311.0432
R=61002
362.9261
R=56002294.9382
R=59002273.1666
R=56500
320.0435
R=61800
255.7743
R=37300
[M + Na]+
SI Fig.S3: HRMS spectrum of [4].
S11
1H NMR spectra of [1]:
SI Fig.S4: 1H NMR spectra of [1] in DMSO-d6 recorded in 500 MHz.
S12
13C NMR spectra of [1]:
SI Fig.S5: 13
C NMR spectra of [1] in DMSO-d6 recorded in 400 MHz.
S13
Mass spectra of [1]:
[M + H]+
[M + Na]+
SI Fig.S6: HRMS spectrum of [1].
S14
1H NMR spectra of [2]:
SI Fig.S7: 1H NMR spectra of [2] in DMSO-d6 recorded in 400 MHz.
S15
13C NMR spectra of [2]:
SI Fig.S8: 13
C NMR spectra of [2] in DMSO-d6 recorded in 500 MHz.
S16
Mass spectra of [2]:
[M + H]+
[M + Na]+
SI Fig.S9: HRMS Spectrum of [2].
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300 350 400 450
0.00
0.25
0.50
384
355
365
Ab
so
rba
nc
e
(nm)
THF
90% H2O
372
300 350 400 450
0.14
0.28
0.42
0.56
0.70
Ab
so
rba
nc
e
(nm)
THF, RT
70oC
60oC
50oC
40oC
30oC
20oC
10oC
UV-Vis absorption spectra of [1]:
SI Fig.S10: Absorption spectra of 1 in pure THF and THF-water (1:9; v/v) mixture solution.
Concentration used 10 μM.
Variable-temperature UV-Vis absorption spectra of [1]:
SI Fig.S11: Variable-temperature UV-Vis spectra of 1 (concentration used 10 μM) in THF-water
(3:7; v/v). Temperature varied from 10-70°C.
S18
0 150 300 450
50
75
100W
t lo
ss
%
Temperature (oC)
Compound-1
275 330 385 440
0
200
400
600
800
Inte
ns
ity
(a
.u.)
(nm)
Ems
= 454 nm
Ems
= 487 nm
(b)
275 330 385 4400.00
0.15
0.30
0.45
Ab
so
rba
nc
e
nm)
THF
(a)
Weight-loss profile (TGA plot) of [1]:
SI Fig.S12: Weight-loss profile for 1 obtained using thermogravimetric analysis (TGA).
Comparisons between absorption and excitation spectra of [1]:
SI Fig.S13: a) Absorption and b) fluorescence excitation spectra (λEms = 454 and 487 nm) of 1 in
THF.
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275 330 385 4400.00
0.15
0.30
0.45A
bs
orb
an
ce
(nm)
10% H2O
(c)
275 330 385 4400
30
60
90
120
Inte
ns
ity
(a
.u.)
nm)
Ems
= 487 nm(d)
300 360 420
60
120
180
240
Inte
ns
ity
(a
.u.)
(nm)
Ems
= 468 nm
Ems
= 551 nm
(f)
275 330 385 4400.0
0.1
0.2
0.3
0.4
Ab
so
rba
nc
e
(nm)
50% H2O
(e)
SI Fig.S14: a) Absorption and b) fluorescence excitation spectra (λEms = 487 nm) of 1 in THF-
water (9:1; v/v).
SI Fig.S15: a) Absorption and b) fluorescence excitation spectra (λEms = 468 and 551 nm) of 1 in
THF-water (1:1; v/v).
S20
275 330 385 440
0.00
0.11
0.22
0.33
Ab
so
rba
nc
e
(nm)
90% H2O
(g)
300 360 4200
60
120
180
240
Inte
ns
ity
(a
.u.)
(nm)
Ems
= 551 nm(h)
280 320 360 4000.0
0.2
0.4
0.6
Ab
so
rba
nc
e
(nm)
Compound-2
SI Fig.S16: a) Absorption and b) fluorescence excitation spectra (λEms = 551 nm) of 1 in THF-
water (1:9; v/v).
UV-Vis absorption spectra of [2].
SI Fig.S17: Absorption spectra of 2 in pure THF. Concentration used 10 μM.
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450 500 5500
5
10
15
20
Inte
ns
ity
(a
.u.)
nm)
0
10
20
30
40
50
60
70
80
90
95
99
Water fraction (%)
400 500 600 7000
200
400
600
Inte
ns
ity
(a
.u.)
(nm)
DMF
MeOH
Toluene
THF
Solvent dependent emission spectra of [2]:
SI Fig.S18: luminescence spectra of 2 (10 µM) in THF and THF-water mixed solvent medium
(Ext = 306 nm was used for luminescence studies).
Emission spectra of [1] in different polarities of solvents:
SI Fig.S19: Emission spectra of 1 (1 μM) in DMF, MeOH, THF and Toluene. λExt = 365 nm.
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1581 cm-1
1720 cm-1
1643 cm-1
1589 cm-1
1619 cm-1
1656 cm-1
3425 cm-1
1702 cm-1
3500 3000 1680 1400
Compound 2
Wavenumber (cm-1)
Compound 1
% T1606 cm
-1
Comparisons of FT-IR spectrum between compound [1] and [2]:
SI Fig.S20: Comparisons of FT-IR spectra of compound 1 and 2 at room temperature.
SI Table.S1: Important FT-IR frequency obtained from compound 1 and 2.
Compound-1 3425 cm-1
(-OHhydrogen bonded), 1702 cm-1
(-COOHstr), 1656 cm-1
(-C=Nstr),
1619 cm-1
(-C=Oamide, str), 1589 cm-1
(-NHamide, str)
Compound-2 1720 cm-1
(-COOEtstr), 1643 cm-1
(-C=Oamide,str), 1606 cm-1
(-C=Nstr), 1581
cm-1
(-NHamide,str)
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0%
H2O
10%
H2O
20%
H2O
30%
H2O
40%
H2O
50%
H2O
60%
H2O
70%
H2O
80%
H2O
90%
H2O
99%
H2O
(a)
(a) (b) (c)
Gelation study of [2]:
SI Fig.S21: Photographs of THF solution of compound 2 (a) immediately after dissolving the
compound (16.0 mg/mL of THF) by gentle heating; (b) after 24 hrs upon cooling to room
temperature; (c) under 365 nm UV light. Indicating Under identical condition or even higher
concentration [compare to compound- 1 (10.0 mg/ mL of THF)] compound-2 is unable to give
gel.
Photographs showing the changes of emission color of 1:
SI Fig.S22: (a) Photographs showing the changes of emission color with gradual increase of
water (%) into THF solution of 1.
S24
J-type lamellar arrangement
≡S
ingle
fib
ers
THF (Solvent ≡ )
Solvent entrapment
Gel network
THF gel of [1]
Schematic route for gelation of [1]:
SI Fig.S23: A schematic route for the synthesis of THF gel of 1 and its molecular arrangement.
S25
1 2 3 4
25
50
75
Inte
ns
ity
(a
.u.)
degree)
(a)
10 20 301
2
3
Inte
ns
ity
(a.u
.)
degree)
(b)
Rheological property of [1]:
SI Fig.S24: Dynamic frequency sweep measurement of storage modulus (G´) and loss modulus
(G´´) for THF gel (1.0 wt. %) of 1. Strain used was 0.1%.
XRPD pattern of [1]:
SI Fig.S25: (a) Small angle and (b) wide angle XRPD diffraction pattern of 1 in xerogel state.
1.0 1.5
2.7
3.0
3.3
log
(G"/P
a)
log
(G'/P
a)
log(frequency/ rad S-1)
log G'
2.7
3.0
3.3
log G"
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-10 -5 0 5 10
-0.4
-0.2
0.0
0.2
0.4
Cu
rre
nt(
)
Voltage (V)
I-V characteristic plot of [1]:
SI Fig.S26: I-V characteristic plot obtained from 1.
Solvent dependent FESEM images of [1]:
(a) (b) (c) (d)
SI Fig.S27: Solvent dependent FESEM images of 1 having (a) 0, (b) 10, (c) 50 and (d), 90 %
water content in THF. Concentration used was 100μM.