Supporting Information
A Dipyrenyl Calixazacrown Chemosensor for Mg2+
Abdelwaheb Hamdi,*,† Sang Hoon Kim,§ Rym Abidi,† Pierre Thuéry,Ϯ Jong Seung Kim,*,§
and Jacques Vicens*,#
†
Laboratoire d’Application de la Chimie aux Ressources et Substances Naturelles et à
l’Environnement (LACReSNE) , Faculté des Sciences de Bizerte, Tunis
§Department of Chemistry, Korea University, Seoul 136-701, Korea
Ϯ CEA, IRAMIS, SCM, LCCEf, CNRS URA 331, Bât. 125, 91191 Gif-sur-Yvette, France
#
IPHC-ULP-ECPM-CNRS URA 7178, 25 rue Becquerel, F-67087, Strasbourg Cédex, France
hamdi_chimie@yahoo.fr;jongskim@korea.ac.kr;vicens@chimie.u-strasbg.fr
Contents
General Experimental Methods.
Page 2
Figure S1. 1H NMR spectrum of 5
Page 3
Figure S2. 1H NMR spectrum of 3
Page 4
Figure S3. 1H NMR spectrum of 4
Page 5
Figure S4. MALDI TOF spectrum of 5
Page 6
Figure S5. MALDI TOF spectrum of 3
Page 7
Figure S6. MALDI TOF spectrum of 4
Page 8
Figure S7. ORTEP View of 5·4CH3OH.
Page 9
Figure S8. Job’s plot of complexation of 4 and Mg2+
Page 10
Figure S9. 1H NMR spectrum of 4 in CDCl3
Page 11
Figure S10. 1H NMR spectrum of 4-Mg2+ in CD3CN
Page 12
Figure S11. MALDI TOF spectrum of 4-Mg2+ in CD3CN
Page 13
1
General Experimental Methods. All reagents and solvents for synthesis were commercial
and used without further purification. All the reactions were performed under a nitrogen
atmosphere. TLCs were carried out on Silica gel 60 F254 (Merck 1.05554.0001). SiO2
(Geduran 1.11567) was used for column chromatography. 1H NMR spectra were recorded at
293 K, unless otherwise stated, using a 300 MHz Bruker SY 200 or a 400 MHz Varian Unity
Plus Spectrometer. Shifts are referenced relative to the internal reference standard,
tetramethylsilane (TMS). Coupling constants J are given in Hz. MALDI TOF mass spectra
were measured on a Biflex Bruker. Melting points were measured using an electrothermal
Mel-temp® melting point apparatus and are reported uncorrected. Elemental analyses were
carried out at the Service de Microanalyse de l’ULP à Strasbourg. Dimethylester p-tertbutylcalix[4]arene (6)20
and N-(1-pyrenemethyl) chloroacetamide (7)21 were prepared
according to literature.
2
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
Figure S1. 1H NMR spectrum of 5
3
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
Figure S2. 1H NMR spectrum of 3
4
21.9
4.0
4.1
2.0
3.4
6.0
7.9
8.0
12.0
18.9
19.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
Figure S3. 1H NMR spectrum of 4
5
Figure S4. MALDI TOF spectrum of 5
6
Figure S5. MALDI TOF spectrum of 3
7
Figure S6. MALDI TOF spectrum of 4
8
X-ray Structure of 5·4CH3OH
Figure S7. ORTEP View of 5·4CH3OH. The carbon-bound hydrogen atoms are omitted.
Hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 30%
probability level
Description of the crystal feature. The molecule of 5 is devoid of any symmetry element.
The four aromatic rings make dihedral angles of 71.39(6), 51.79(7), 74.33(7) and 51.35(6)°
with the mean plane defined by the four methylenic carbon atoms of the calixarene (rms
deviation 0.035 Å). The rings bearing the crown are more tilted than the others, as usual in
such compounds.21b Two intramolecular hydrogen bonds link the phenolic groups (O3 and
O6) to the neighbouring, crown-bearing oxygen atoms O1 and O4, while two other hydrogen
bonds connect two amine groups (N1 and N4) to the phenolic oxygen atoms O3 and O6. Such
intramolecular hydrogen bonding has been observed in other calixazacrowns.21b The bonds
between the two amines and the phenolic groups result in a buckling of the azacrown, with the
central part of the chain being roughly perpendicular to the O1–O4 line. Three intermolecular
hydrogen bonds are also formed, between three methanol solvent molecules and the carbonyl
atoms O2 and O5 and the nitrogen atom N3, while the fourth methanol molecule is included
in the cavity of 5.
9
[4] / [4] + [Mg2+]
Figure S8. Job’s plot of a 1:1 complex between 4 and Mg2+ion, where the difference
in fluorescence intensity at 395 nm was plotted against the mole fraction of 4 at an invariant
total concentration of 5 μM in CH3CN
10
PPM
9.0
8.0
7.0
file: C:\Documents and Settings\USER\ 바 탕 화 면 \NMR\sangdipyreneOnly.fid\fid block# 1 expt: "s2pul"
transmitter freq.: 300.177924 MHz
time domain size: 17984 points
width: 4500.45 Hz = 14.992608 ppm = 0.250247 Hz/pt
number of scans: 40
6.0
5.0
4.0
3.0
36.12
7.789
12.19
8.052
4.018
5.936
1.887
5.999
2.128
8.315
STANDARD 1H OBSERVE
7.874
SpinWorks 2.5:
2.0
1.0
0.0
freq. of 0 ppm: 300.176449 MHz
processed size: 32768 complex points
LB: 0.000 GB: 0.0000
Figure S9. 1H NMR spectrum of 4 in CD3CN
11
8.0
7.0
file: C:\Documents and Settings\USER\ 바 탕 화 면 \NMR\sangdipyreneMgOnly.fid\fid block# 1 expt: "s2pul"
transmitter freq.: 300.177924 MHz
time domain size: 17984 points
width: 4500.45 Hz = 14.992608 ppm = 0.250247 Hz/pt
number of scans: 40
6.0
5.0
4.0
3.0
37.81
3.985
3.807
2.327
3.804
1.931
1.860
4.318
4.359
3.878
9.0
2.009
PPM
18.01
STANDARD 1H OBSERVE
7.858
SpinWorks 2.5:
2.0
1.0
0.0
freq. of 0 ppm: 300.176448 MHz
processed size: 32768 complex points
LB: 0.000 GB: 0.0000
Figure S10. 1H NMR spectrum of 4-Mg2+ in CD3CN
12
Figure S11. MALDI TOF spectrum of 4-Mg2+ in CD3CN
13