Electronic Supplementary Material (ESI) for Photochemical & Photobiological Sciences.

This journal is © The Royal Society of Chemistry and Owner Societies 2017

- Electronic Supplementary Information -

Photoluminescent responses of graphene quantum

dots toward organic bases and an acid

Kaho Suzuki, Kairi Yamato, Ryo Sekiya, and Takeharu Haino*

Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama,

Higashi-Hiroshima, Hiroshima 739-8526 Japan

*To whom correspondence should be addressed.

[email protected]

S1
 Contents

Experimental Section

• General ··· S3
• DLS analysis ··· S3
• Computational Detail ··· S3

Supporting Figures and Tables

• Figure S1. UV/vis absorption and photoluminescence spectra of GQD-1 ··· S4

• Figure S2. UV/vis absorption and photoluminescence titration experiments (amine: 3) ··· S4
• Figure S3. UV/vis absorption and photoluminescence titration experiments (amine: 4) ··· S4
• Figure S4. UV/vis absorption and photoluminescence titration experiments (amine: 6) ··· S5
• Figure S5. UV/vis absorption and photoluminescence titration experiments (NaOH) ··· S5
• Figure S6. 1H NMR titration experiment (amine: 6) in chloroform-d1 ··· S5
• Figure S7. DQF-COSY spectrum of 2 in chloroform-d1 ··· S6
• Figure S8. DQF-COSY spectrum of 3 in chloroform-d1 ··· S6
• Table S1. The energy levels of the HOMO and LUMO of 2–6 ··· S7

Cartesian Coordinates

• Cartesian Coordinates of 2 ··· S8

• Cartesian Coordinates of 3 ··· S9
• Cartesian Coordinates of 4 ··· S10
• Cartesian Coordinates of 5 ··· S11
• Cartesian Coordinates of 6 ··· S11

References
• References ··· S12

S2
 Experimental Section

General

All chemicals and solvents were purchased from Kanto Chemical Co., Ltd., Wako Pure Chemical Co., Ltd.,
Tokyo Kasei Kogyo Co., Ltd., and Sigma-Aldrich Co., Ltd., and were used as received without further
purification. 1H, and 13CNMR spectra were recorded on a VARIAN 300 MHz spectrometer. Chemical shifts are
quoted as parts per million (ppm) relative to chloroform (CDCl3,  = 7.26 ppm for 1H and 77.16 ppm for 13C). IR
absorption spectra were recorded on a JASCO FT/IR-4600 spectrometer using pellets in KBr. UV/vis absorption
spectra were recorded on a JASCO V-560 spectrophotometer. Emission spectra were recorded on a JASCO FP-
6500 spectrophotometer. GQD-1 were synthesized by the method reported previously.[1]

Computational Details

Geometry optimizations for 2–6 were performed by Gaussian 09 using B3LYP/6-31G level of theory.[2] The
energy levels of the HOMO and LUMO of 2–6 are listed in Table S1. The Cartesian coordinates of the energy-
minimized conformations of 2–6 are listed in Tables S2-S6.

S3
 Supporting Figures and Tables

(a) 1.0 (b)

360 nm
380 nm

Fluorescence Intensity
400 nm
420 nm
440 nm
Absorbance

460 nm
480 nm
0.5

0
300 400 500 600 700 300 400 500 600 700
Wavelength / nm Wavelength / nm

Figure S1. (a) UV/vis absorption and (b) photoluminescence (ex = 360, 380, 400, 420, 440, 460, and 480 nm)
spectra of GQD-1 in 1,2-dichlroethane at 293 K.

Figure S2. (a) UV/vis absorption and (b) photoluminescence (ex = 360 nm) titration experiments of GQD-1 in
1,2-dichloroethane at 293 K. Amine: 1,8-diazabicyclo[5.4.0]undec-7-ene (3). (c) Stern-Volmer plot of GQD-1 (
= 450 nm) upon addition of 3.

Figure S3. (a) UV/vis absorption and (b) photoluminescence (ex = 360 nm) titration experiments of GQD-1 in
1,2-dichloroethane at 293 K. Amine: triethylamine (4). (c) Stern-Volmer plot of GQD-1 ( = 450 nm) upon
addition of 3.

S4
Figure S4. (a) UV/vis absorption and (b) photoluminescence (ex = 360 nm) titration experiments of GQD-1 in
1,2-dichloroethane at 293 K. Amine: pyrimidine (6). (c) Stern-Volmer plot of GQD-1 ( = 450 nm) upon addition
of 6.

Figure S5. (a) UV/vis absorption and (b) photoluminescence (ex = 360 nm) titration experiments of GQD-1 in a
mixed solvent of THF and ethanol at 293 K. Base: sodium hydroxide. (c) Stern-Volmer plot of GQD-1 ( = 450
nm) upon addition of base.

Figure S6. 1H NMR (300 MHz, 293 K, chloroform-d1) titration experiment of GQD-1. Amine: pyrimidine (6).
The concentration of 6 was 31.84 mM throughout the experiment. The concentration of GQD-1 were (i) 0, (ii)
0.46, (iii) 0.93, (iv) 1.87, and (v) 3.74 mg mL–1.

S5
Figure S7. DQF-COSY (300 MHz, 293 K, chloroform-d1) of 1.5-diazabicyclo[4.3.0]non-5-ene (2).

f ha g c,d
e b
0.5

1.0

1.5

2.0
δ / ppm

2.5

3.0

3.5
a h
b
N g
c 4.0
N f
d e
4.5
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
δ / ppm

Figure S8. DQF-COSY (300 MHz, 293 K, chloroform-d1) of 1,8-diazabicyclo[5.4.0]undec-7-ene (3).

S6
Table S1. The energy levels of the HOMO+1, HOMO, LUMO, and LUMO+1 of 2–6 calculated by Gaussian 09
using B3LYP/6-31G(d,p) level of theory.
Base HOMO+1 / hartree HOMO / hartree LUMO / hartree LUMO+1 / hartree
2 –0.22446 –0.19968 +0.04325 +0.08584
3 –0.22085 –0.19642 +0.04519 +0.06936
4 –0.32065 –0.20417 +0.09184 +0.10894
5 –0.26185 –0.25251 –0.02312 –0.01034
6 –0.28997 –0.25465 –0.04299 –0.03085
HOMO+1 / eV HOMO / eV LUMO / eV LUMO+1 / eV
2 –6.1078 –5.4335 +1.1769 +2.3358
3 –6.0095 –5.3448 +1.2297 +1.8874
4 –8.7272 –5.5557 +2.4991 +2.9644
5 –7.1252 –6.8710 –0.6291 –0.2814
6 –7.8904 –6.9293 –1.1698 –0.8395
1 harteree = 27.211 eV

S7
 Cartesian Coordinates

Table S2. Cartesian coordinates of the optimized structure of 2 at the B3LYP/6-31G(d,p) level.
----------------------------------------------------------------------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
----------------------------------------------------------------------------------------------------------------------------------------
1 6 0 1.569684 1.181220 -0.185106
2 6 0 2.466481 0.017521 0.281678
3 6 0 1.631262 -1.234551 -0.048824
4 1 0 1.717559 2.096642 0.400465
5 1 0 1.754772 1.433012 -1.243911
6 1 0 3.445932 0.027126 -0.202544
7 1 0 2.624038 0.091484 1.362366
8 1 0 1.776956 -2.066039 0.643780
9 1 0 1.852512 -1.608035 -1.056050
10 6 0 -2.137407 -0.830842 -0.128515
11 6 0 -2.151260 0.617143 0.390968
12 6 0 -0.979572 1.412396 -0.197876
13 1 0 -2.857008 -1.429573 0.442885
14 1 0 -2.490102 -0.855156 -1.170943
15 1 0 -2.055792 0.613129 1.482959
16 1 0 -3.099539 1.108096 0.146885
17 1 0 -0.880798 2.388299 0.293786
18 1 0 -1.143677 1.606501 -1.271522
19 6 0 0.195403 -0.738670 -0.025297
20 7 0 0.232516 0.647547 0.015242
21 7 0 -0.834288 -1.497659 -0.065289
----------------------------------------------------------------------------------------------------------------------------------------

S8
Table S3. Cartesian coordinates of the optimized structure of 3 at the B3LYP/6-31G(d,p) level.
----------------------------------------------------------------------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
----------------------------------------------------------------------------------------------------------------------------------------
1 6 0 2.597149 -0.768363 0.205507
2 6 0 2.372454 0.645508 0.751839
3 6 0 1.445136 1.410606 -0.190834
4 1 0 3.190301 -1.358311 0.914302
5 1 0 3.192533 -0.716371 -0.719964
6 1 0 3.317311 1.187828 0.866653
7 1 0 1.909875 0.577503 1.743879
8 1 0 1.991041 1.707496 -1.099981
9 1 0 1.095356 2.334524 0.285903
10 6 0 -0.954865 1.279000 -0.904078
11 6 0 -1.987395 1.355563 0.243144
12 6 0 -2.036377 0.078357 1.095710
13 6 0 -2.133165 -1.242760 0.314053
14 6 0 -0.970595 -1.524010 -0.685107
15 1 0 -0.691459 2.286213 -1.242645
16 1 0 -1.404643 0.783745 -1.770343
17 1 0 -1.753906 2.204079 0.898480
18 1 0 -2.971937 1.565241 -0.195488
19 1 0 -1.138388 0.042189 1.723521
20 1 0 -2.884604 0.145070 1.787568
21 1 0 -3.087177 -1.285592 -0.226322
22 1 0 -2.162870 -2.055599 1.047834
23 1 0 -1.292922 -1.290500 -1.706801
24 1 0 -0.714870 -2.584181 -0.672416
25 7 0 0.283078 0.594132 -0.545363
26 6 0 0.325256 -0.786474 -0.398075
27 7 0 1.354175 -1.483832 -0.058513
----------------------------------------------------------------------------------------------------------------------------------------

S9
Table S4. Cartesian coordinates of the optimized structure of 4 at the B3LYP/6-31G(d,p) level.
----------------------------------------------------------------------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
----------------------------------------------------------------------------------------------------------------------------------------
1 6 0 -1.928636 1.524753 -0.437753
2 1 0 -2.682909 0.732182 -0.407871
3 1 0 -2.411997 2.449403 -0.104492
4 1 0 -1.615405 1.649359 -1.478300
5 7 0 0.000386 0.000789 0.019178
6 6 0 -0.359628 -2.431266 -0.437579
7 6 0 -0.684318 -1.225974 0.446370
8 1 0 -1.762407 -1.045772 0.395705
9 1 0 -0.464477 -1.461749 1.506140
10 6 0 -0.720303 1.207405 0.444637
11 1 0 -0.026345 2.051689 0.390897
12 1 0 -1.032634 1.137021 1.505111
13 6 0 1.405104 0.021527 0.446450
14 1 0 1.787512 -1.002486 0.397501
15 1 0 1.499269 0.331248 1.505816
16 6 0 2.287595 0.903367 -0.438446
17 1 0 3.329389 0.858894 -0.103187
18 1 0 1.981007 1.953775 -0.414234
19 1 0 2.240218 0.565026 -1.477521
20 1 0 -0.918696 -3.311642 -0.102794
21 1 0 0.703644 -2.689910 -0.412060
22 1 0 -0.627752 -2.221432 -1.477029
----------------------------------------------------------------------------------------------------------------------------------------

S10
Table S5. Cartesian coordinates of the optimized structure of 5 at the B3LYP/6-31G(d,p) level.
----------------------------------------------------------------------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
----------------------------------------------------------------------------------------------------------------------------------------
1 6 0 1.197699 0.674071 0.000001
2 6 0 1.143063 -0.720627 0.000000
3 6 0 -1.141366 -0.723246 0.000001
4 6 0 -1.199052 0.671840 0.000001
5 6 0 -0.001591 1.385366 0.000000
6 1 0 2.155685 1.184559 -0.000001
7 1 0 2.061707 -1.304941 0.000001
8 1 0 -2.059013 -1.309161 0.000001
9 1 0 -2.158359 1.179842 -0.000002
10 1 0 -0.002449 2.471638 -0.000005
11 7 0 0.001416 -1.420909 -0.000001
----------------------------------------------------------------------------------------------------------------------------------------

Table S6. Cartesian coordinates of the optimized structure of 6 at the B3LYP/6-31G(d,p) level.
----------------------------------------------------------------------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
----------------------------------------------------------------------------------------------------------------------------------------
1 6 0 -1.309629 0.003347 -0.000036
2 6 0 0.619154 -1.186117 0.000006
3 6 0 1.356270 -0.003120 0.000001
4 6 0 0.625619 1.182843 0.000003
5 1 0 -2.397929 0.005936 0.000085
6 1 0 1.113687 -2.156099 -0.000004
7 1 0 2.440825 -0.006311 -0.000024
8 1 0 1.124174 2.150744 0.000008
9 7 0 -0.719246 -1.197288 0.000007
10 7 0 -0.713503 1.200717 0.000006
----------------------------------------------------------------------------------------------------------------------------------------

S11
 References

[1] R. Sekiya, Y. Uemura, H. Naito, K. Naka, and T. Haino, Chem. Eur. J. 2016, 22, 8198–8206.
[2] Gaussian 09, Revision C.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.;
Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li,
X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota,
K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.;
Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.;
Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.;
Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J.
W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich,
S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc.,
Wallingford CT, 2009.

S12