Synthesis, characterization and selective Cu2+ recognition of novel E– and Z–stilbenophanes

Article abstract of DOI:10.1080/10610278.2018.1528010

We have demonstrated the synthesis and characterization of novel E- and Z-stilbenophanes via four reaction steps. X-ray structure analysis showed that the p-electrons of the double bonds and the oxygen atoms pointing towards the center of a cavity of Z-isomer. Both isomers recognize selectively Cu²⁺ ions over other competing metal ions as measured by UV-vis titration by the detection limit 10–12?μM. The 1:1 ratio complex formation was confirmed by HRMS analysis. Theoretical calculations based on GIAO and CMAD approaches and ¹H NMR analysis confirmed the UV-vis data of Z-isomer.

Full text of DOI:10.1080/10610278.2018.1528010

Supramolecular Chemistry
ISSN: 1061-0278 (Print) 1029-0478 (Online) Journal homepage: http://www.tandfonline.com/loi/gsch20
Synthesis, characterization and selective Cu2+
recognition of novel E– and Z–stilbenophanes
Hossein Reza Darabi, Leila Sobhani, Saeed Rastgar, Kioumars Aghapoor,
Saeed K. Amini, Reza Zadmard, Khosrow Jadidi & Behrouz Notash
To cite this article: Hossein Reza Darabi, Leila Sobhani, Saeed Rastgar, Kioumars Aghapoor,
Saeed K. Amini, Reza Zadmard, Khosrow Jadidi & Behrouz Notash (2018): Synthesis,
characterization and selective Cu2+ recognition of novel E– and Z–stilbenophanes, Supramolecular
Chemistry, DOI: 10.1080/10610278.2018.1528010
To link to this article: https://doi.org/10.1080/10610278.2018.1528010
View supplementary material
Published online: 27 Sep 2018.
Submit your article to this journal
View Crossmark data
Full Terms & Conditions of access and use can be found at
http://www.tandfonline.com/action/journalInformation?journalCode=gsch20

SUPRAMOLECULAR CHEMISTRY
https://doi.org/10.1080/10610278.2018.1528010
Synthesis, characterization and selective Cu2+ recognition of novel E– and
Z–stilbenophanes
Hossein Reza Darabia, Leila Sobhania, Saeed Rastgara, Kioumars Aghapoora, Saeed K. Aminia, Reza Zadmarda,
Khosrow Jadidib and Behrouz Notashb
aNano & Organic Synthesis Lab, Chemistry & Chemical Engineering Research Center of Iran, Tehran, Iran; bDepartment of Chemistry, Shahid
Beheshti University, G.C. Tehran, Iran
ABSTRACT
ARTICLE HISTORY
Received 16 May 2018
Accepted 16 September 2018
We have demonstrated the synthesis and characterization of novel E- and Z-stilbenophanes via
four reaction steps. X-ray structure analysis showed that the p-electrons of the double bonds and
the oxygen atoms pointing towards the center of a cavity of Z-isomer. Both isomers recognize
selectively Cu2+ ions over other competing metal ions as measured by UV-vis titration by the
detection limit 10–12 µM. The 1:1 ratio complex formation was confirmed by HRMS analysis.
KEYWORDS
Stilbenophane; synthesis;
Cu2+ ion recognition;
theoretical calculations
1
Theoretical calculations based on GIAO and CMAD approaches and H NMR analysis confirmed
the UV-vis data of Z-isomer.
Introduction
physicochemical and molecular recognition (6–10) to
biological activity (11, 12).
Supramolecular chemistry is a relatively young area of
interdisciplinary field of science which is located at the
intersection of chemistry, biology, and physics (1–5).
The preparation method, characterization and applica-
tion of receptors are the principles of supramolecular
chemistry to make nonbonding supramolecular interac-
tions with substrates.
One of the defining concepts of supramolecular
chemistry is host–guest chemistry in which the non-
covalent interactions leads to the formation of unique
structural complexes. The binding ability of a host is
depended to its size, shape, rigidity, receptor sites and
the cavity. Therefore, to tune the binding ability of a
host, a careful design of the host is needed.
In the past few years, we have prepared a series of
2,2ʹ-stilbenophanes 1 and 2 (Scheme 1) which are
resulted from a combination of alkyl chain length and
the configuration of alkene of stilbene moeity (13–20).
The application of these molecules as sensor of metal
ions has been successful because of the suitable shape,
stereochemistry and cavity size of host. For example,
the host 1c recognizes Li+ ions (14), while Z,Z-1b (16)
and E,E-1a (18) host the silver ions. On the other hand,
stilbenophanes 1b and 1c are suitable hosts for Pd2+
ions as evidenced from their self-activation in Wacker
oxidation (19, 20).
Herein, we wish to report the synthesis and character-
ization of new stilbenophanes E-1d and Z-1d. Based on the
ability of crown ethers and as well as π-electron systems to
host metal ions (21–23), we also studied the host-guest
chemistry of 1. Accordingly, both isomers exhibited selec-
tive optical sensing toward Cu2+ ions among various metal
Stilbenophanes are macrocyclic molecules which
accomplished by linking the various positions of stil-
bene moiety with an appropriate bridging moiety. They
have attracted attention in various fields from
CONTACT Hossein Reza Darabi
darabi@ccerci.ac.ir; r_darabi@yahoo.com
Nano & Organic Synthesis Lab, Chemistry & Chemical Engineering
Research Center of Iran, Pajoohesh Blvd., 17th Km of Tehran–Karaj Highway, Tehran 14968-13151, Iran
supplemental data for this article can be accessed here.
© 2018 Informa UK Limited, trading as Taylor & Francis Group

2
H. R. DARABI ET AL.
In both isomers, the alkene protons appear as one
sharp singlet. The cis-geometry was assigned to the
isomer with lower chemical shift value for the vinylic
protons (7.37 ppm for E-1d and 6.60 ppm for Z-1d).
Moreover, the chemical shifts of aromatic hydrogens of
E-1d are more deshielded and expanded than those of
Z-1d (6.80–7.50 ppm for E-1d and 6.65–7.45 ppm for
Z-1d). The expected peak of each methylene group was
observed as singlet. The number of observed signals
agrees with the expected number of carbons in both
isomers.
Scheme 1. A series of prepared stilbenophanes 1 in our lab.
X-ray crystallographic analysis at 298K confirmed the
molecular structure of Z-1d and determined its geome-
try (27). Two different views of the molecules are shown
in Figure 1 and Figure S16. The compound crystallizes
in the monoclinic system and P21/c space group. The
ions. The existence of bromines on the two sides of mole-
cular ring gives this chance to make a polymer (24–26) for
the selective adsorption of Cu2+ ions.
Results and discussion
The four steps synthesis of E-1d and Z-1d are shown in
Scheme 2. The carbonyl groups of dialdehyde 5 were
reduced by sodium borohydride to give 4 in 95% yield.
The dibenzil 4 was then treated with excess amount of
bromine in CH2Cl2 to give brominated product of 3 in
95% yield, which in turn, was coupled with 2.3 equiv. of
salisaldehyde in the presence of K2CO3 in DMF to pro-
vide the precursor 2 in 92% yield.
Finally, the intramolecular coupling of the dialde-
hyde 2 with low-valent titanium, prepared from reflux-
ing TiCl4 and Zn in THF, gave a mixture of Z-1d and
E-1d. The crude products were purified on silica gel
eluted with hexane–ethyl acetate (7:3) to afford, in
order of elution, Z-1d and E-1d in 35% and 30% yield,
respectively.
The structures of the cyclophanes E-1d and Z-1d
were determined by NMR spectroscopic data. Both iso-
mers are highly soluble in common solvents. Therefore,
1
we measured their H and 13C NMR spectra in CDCl3
and found the asymmetric structure of products
(Figures S11-S15).
Figure 1. The molecular structure of Z-1d.
Scheme 2. The synthesis of E- and Z-stilbenophane 1d.

SUPRAMOLECULAR CHEMISTRY
3
ethene bridge [C (21)-C (22)] exhibits a cis configura-
tion, in agreement with the 1H NMR spectrum, with
considerably widened bond angles 129.8 (7)º for C
(20)-C (21)-C (22). As shown in Figure S16, the molecular
structure of Z-1d contains a rectangular cavity with
dimensions that are defined by the distance between
the two facing oxygen atoms (~ 4.0 Å). Two facing
phenyl units are almost parallel with respect to each
other with a torsion angle of about 158 with a weak π–
π interaction (4.3 Å). The phenylene rings of stilbene
moiety are rotated by about 40-45º with respect to
double bond. As a consequence, the π-electrons of
both the double bonds and the oxygen atoms point
into the cavity to accommodate the guest. In contrast,
bromide atoms are out of cavity.
ions, the absorbance intensity at 280 nm was gradu-
ally increased, while peak around 330 nm was
decreased. It means that conjugation of stilbene moi-
ety of E-1d, unlike Z-1d, are decreased during the
complex formation. The isosbestic point in the
absorption spectra of both isomers was observed to
clearly indicate the formation of receptor-cation com-
plex in the solution. From the binding constant cal-
culation of both isomers of 1d with Cu2+ (28), the
obtained detection limit of both isomers for Cu2+ ions
were found to be 10–12 µM which is lower than the
maximum allowable level of Cu2+ions (31.5 µM) in
drinking water set by the WHO (29).
The optical response arises from the 1:1 complexa-
tion of 1d with the Cu2+ ions as evidenced from high
resolution mass spectrum (HRMS) data showing a peak
at m/z 654.9365 (Figures S10 and S20).
It is noteworthy to mention that the McMurry cou-
pling of the non-brominated dialdehyde 2ʹ did not give
any amounts of stilbenophanes 1ʹ (Figures S17-19). It
means that the bromines play an important role on the
intramolecular cyclization of the dialdehyde 2.
The 1H-NMR spectra were recorded in DMSO-d6 and the
assignments of Z-1d and Z-1d@Cu2+ are shown in Figure 3.
1
It was found that all H NMR signals of Z-1d are shifted
The UV-vis spectra of compounds E-1d and Z-1d
exhibited two and one main absorbance bands, respec-
tively. To evaluate the binding ability of both isomers
toward different transition metal ions, the UV-vis spec-
trophotometric titration were carried out by the addi-
tion of metal ions to ligands 1 in a quartz cell in CH3CN
solutions. Except Cu2+, no noticeable changes were
observed with other metals (Li+, Na+, Ni2+, Co2+, Cu+,
Pd2+, Hg2+, Fe2+, Fe3+ and Pb2+) under the same
conditions.
slightly downfield (ca 0.06–0.09 ppm) upon complexation
with CuCl2. Consequently, the results of both UV-vis and
1H-NMR analysis indicates that conjugation between two
aryl groups are increased during the complex formation.
To obtain more information about the structure of
complex Z-1d@Cu2+, our attempts to obtain suitable
single crystals of complex for X-ray studies failed. On
the other hand, the data obtained by NMR and UV-vis
analysis need more support to show the certain posi-
tion of Cu2+ ion in resultant complex.
The addition of CuCl2 to solution of E-1d and Z-1d
induced a dramatic change in the UV-vis spectrum
which are diagnostic for changes in the electronic
structure of the molecules (Figure 2). While absor-
bance intensity of Z-1d at 280 was gradually
decreased, a new peak around 310 nm was appeared
upon gradual addition of Cu2+ ions. On the other
hand, changes in the UV-vis spectrum of E-1d was
different with those of Z-1d. upon addition of Cu2+
To this end, we resort to some computational results to
circumvent this problem by using all probable positions
of Cu2+ ion in complex (Table S1 and Figure 4). These
solution state computational results are obtained from
geometry optimization followed by chemical shielding
and excited state calculations. Geometry optimization
and chemical shielding calculations using density func-
tional theory (DFT) employ ONIOM(B3LYP/6–311 + g(d,p):
BP86/TZVP) and B3LYP/6–311 + G(d,p) levels of theory for
Figure 2. UV−vis spectra of (a) Z-1d and (b) E-1d upon addition of Cu2+ in CH3CN.

4
H. R. DARABI ET AL.
1
Figure 3. H NMR spectroscopy of Z-1d (above) and Z-1d@Cu2+ (below) in DMSO-d6.
1:
2:
3:
4:
5:
6:
Figure 4. Optimized geometries of Z-1d@Cu2+. The most probable structures 1–6 are shown.
complex and free ligand states, respectively. The BP86/
TZVP and B3LYP/6–311 + G(d,p) levels of theory are used
for Cu2+ ion and Z-1d in ONIOM calculations, respectively
(Figure 4). Gauge invariant atomic orbital (GIAO) condition
is applied in the chemical shielding calculations (30). Time
dependent DFT (TD-DFT) calculations of excited states are
run at cam-B3LYP/6–31++ G(d,p) level of theory in both
complex and free ligand solutions. The conductor-like
polarizable continuum model (CPCM) is used for chloro-
form solvent (31). All calculations are run using ORCA
software (32). Calculated and experimental chemical
shift values beside calculated relative energies are sum-
marized in Table S1. While relative energies suggest com-
plexes 1 and 2 as most stable and consequently most
probable structures, calculated corrected mean absolute
deviations (CMAD) of shift values do not provide tight
support for this conclusion.
To select one of these two structures as probable
structure in observed experiment, we resort to calcu-
lated UV-Vis spectra obtained from excited state

SUPRAMOLECULAR CHEMISTRY
5
1
calculations. Between the structures 1 and 2, the former
shows similar peaks in accordance with experimental
spectra to suggest the most probable structure of com-
plex under experimental condition. Therefore, the most
possible structure of complex is that Cu2+ is coordi-
nated with oxygen atoms (structure of 2 in Figure 4).
Compound 4: White solid, m.p. = 121-123ºC; H NMR
(500 MHz, DMSO-d6) 7.41 (dd, 2H, PhH), 7.25 (t, 2H, PhH),
7.20 (dd, 2H, PhH), 7.04 (t, 2H, PhH), 5.87 (s, 2H, O- CH2-O),
5.03 (t, 2H, -OH), 4.46 (d, 4H, CH2OH).; 13C NMR (125 MHz,
DMSO) δ 153.6, 132.0, 128.1, 127.8, 122.4, 114.3, 90.9,
58.2.; IR (KBr, cm−1): 3298, 2925, 2864, 1597, 1490, 1457,
1215, 1112, 1043, 1013, 750, 431.
Conclusion
Procedure for the preparation of compounds 3
In conclusion, we have demonstrated the syntheses and
spectral properties of novel E- and Z-stilbenophanes 1d for
the first time. The crystal structure of Z-1d was also
achieved. Both isomers act as colorimetric chemosensors
for Cu2+ ions over other competing metal ions. To estimate
An excess amount of Br2 (1.2 g, 7.72 mmol) was added
to a solution diol 4 (0.5 g, 1.93 mmol) in CH2Cl2 (25 ml)
at room temperature. The dark red solution of reaction
mixture was stirred for 12 h. The progress of reaction
was monitored by TLC. The remained Br2 was quenched
with saturated sodium thiosulfate in H2O. The organic
compounds were extracted with CH2Cl2 (3 × 10 ml) and
were dried over anhydrous NaSO4. After removing sol-
vent, a yellow solid was obtained which was crystallized
by boiling hexane to give a pure white solid of 3 in 95%
yield.
1
the structure of complex, UV-vis and H NMR analysis
together with theoretical calculation of UV-vis analysis
were investigated. Therefore, the most possible structure
of complex is resulted from the coordination between Cu2+
and four oxygen atoms of host.
º
1
Experimental
Compound 3: White solid, m.p. = 177 C; H NMR
(500 MHz, CDCl3) δ 7.50 (d, J = 2.5 Hz, 2H), 7.45 (dd,
J = 8.8, 2.5 Hz, 2H), 7.23 (d, J = 8.8 Hz, 2H), 5.88 (s, 2H),
4.47 (s, 4H). 13C-NMR (125 MHz, CDCl3): 153.7, 133.7,
133.0, 129.2, 116.6, 115.1, 91.1, 27.1.; IR (KBr, cm−1):
2973, 1484, 1310, 1223, 1185, 1144, 1019, 871,
807,612, 519.
Materials and methods
The experiments were conducted in flame-dried glass-
ware under an inert atmosphere of argon unless other-
wise noted. The solvents and reagents used in each
experiment were dried and purified according to
accepted procedures. Melting points are determined on
Büchi 530 and are uncorrected. H and 13C NMR spectra
1
Procedure for the preparation of compounds 2
were recorded on a Bruker 300 and 500. All NMR samples
were run in CDCl3 and chemical shifts are expressed as
ppm relative to internal Me4Si. Mass spectra were
obtained on a Fisons instrument. Column chromatogra-
phy was carried out with the use of Merck Art.7734 kie-
selgel 60, 70–230 mesh ASTM. Tetrahydrofuran (THF) and
CH3CN were freshly distilled under a nitrogen atmosphere
from sodium-benzophenone prior to use. The solutions of
metal ions were performed from their chloride salts and
the stock solution was prepared in CH3CN.
Salisaldehyde (0.21 g, 1.8 mmol) and K2CO3 (0.34 g,
2.5 mmol) was added to DMF (15 ml) at room tempera-
ture and stirred for 1 hour. Then 3 (0.485g, 0.9 mmol)
was added to the mixture and stirred for 3 hours. Then
water (40 ml) was added to the solution and a white
precipitate formed. After it was filtered and a white
solid obtained.
Compound 2: White solid, 1H NMR (300 MHz, CDCl3):
10.48 (s, 2H), 7.86 (dd, 2H), 7.61 (d, J = 1.8 Hz, 2H), 7.50
(t, J = 7.2 Hz, 2H), 7.42 (dd, J = 8.7 Hz, J = 2.1 Hz, 2H),
7.12 (d, J = 8.7 Hz, 2H), 7.06 (d, J = 7.5 Hz, 2H), 6.88 (d,
J = 7.5 Hz, 2H), 5.84 (s, 2H), 5.08 (s, 4H).; 13C-NMR
(75 MHz, CDCl3): 189.3, 160.6, 152.9, 135.9, 132.3,
131.9, 128.7, 128.1, 125.2, 121.3, 116.0, 115.7, 112.8,
91.2, 65.1.; IR (KBr, cm-1): 1600, 1482, 1394, 1283,
1218, 1138, 1100, 993, 831, 758.
General procedure for the preparation of
compounds 4
Sodium borohydride (26.5 mg, 0.7 mmol) was gradually
added to a solution of 5 (0.256 g, 1 mmol) in 1:1 ratio of
THF and C2H5OH (25 ml) while it stirred in the ice-water
bath. After the addition was ended, the reaction mix-
ture was stirred for 2h. After completion of the reaction
as indicated by TLC, H2O (30 ml) was added and a white
precipitate formed. The product was extracted by
EtOAc (30 ml) and gave a pure white powder of 4 in
95% yield.
Procedure for the preparation of compounds 1d
To a stirred suspension of Zinc powder (0.07 g,
1.1 mmol) in 15 ml dry THF, TiCl4 (0.062 ml,
0.55 mmol) was injected slowly at 0 ºC under an

6
H. R. DARABI ET AL.
argon atmosphere. The obtained black suspension
was gradually warmed to room temperature and
then refluxed for 2 h. A solution of dialdehyde 2
(0.15 g, 0.23 mmol) in THF (15 ml) was added drop-
wise to the above reaction mixture at room tem-
perature, and the resulting mixture was refluxed for
an additional 6 h. The reaction mixture was cooled
to room temperature and quenched with 10% aqu-
eous K2CO3 (30ml). The organic layer was separated
and the aqueous suspension was extracted with
diethyl ether. The combined organic layers were
dried over anhydrous MgSO4, filtered, evaporated
and chromatographed on silica gel using a mixture
of ethyl acetate and hexane to afford compound
E-1d (30% yield, rf = 0.62 at 1:8 mixture of ethyl
acetate and hexane) and Z-1d (35% yield, rf = 0.55).
References
(1) Davis, F.; Higson, S. Macrocycles: Construction, Chemistry
and Nanotechnology Applications; Wiley: Chennai, India,
2011.
(2) Brnjas-Kraljevi, J.; Pifat-Mrzljak, G. Supramolecular
Structure and Function 10; Springer: Dordrecht, 2011.
(3) Dodziuk, H.;. Introduction to Supramolecular Chemistry;
Kluwer Academic Publishers: Dordrecht, 2010.
(4) Steed, J.W.; Atwood, J.L. Supramolecular Chemistry;
Wiley: Chichester, 2006.
(5) Ariga, K.; Kunitake, T. Supramolecular Chemistry:
Fundamentals and Applications; Springer-Verlag: Berlin,
Heidelberg, 2006.
(6) Tirado-Rives, J.; Gandour, R.D.; Fronczek, F.R.
Tetrahedron Lett. 1982, 23, 1639–1642. doi:10.1016/
S0040-4039(00)87178-6
(7) Furstner, A.; Seidel, G.; Kopiske, C.; Kruger, C.; Mynott, R.
Liebigs Ann. Chem. 1996, 1996, 655–662.
(8) Futterer, T.; Merz, A.; Lex, J. Angew. Chem., Int. Ed. Engl.
1997, 36, 611–613. doi:10.1002/anie.199706111
º
1
Compound Z-1d. Colorless solid, mp = 168 C; H
1
NMR (300 MHz, CDCl3): H NMR (300 MHz, CDCl3): 7.42
(9) Tirado-Rives, J.; Oliver, M.A.; Fronczek, F.R.; Gandour, R.
D. J. Org. Chem. 1984, 49, 1627–1634. doi:10.1021/
jo00183a026
(10) Ben, I.; Castedo, L.; Saa, J.M.; Seijas, J.A.; Suau, R.; Tojo, G.
J. Org. Chem. 1985, 50, 2236–2240. doi:10.1021/
jo00213a008
(11) Álvarez, R.; López, V.; Mateo, C.; Medarde, M.; Peláez, R.
Chem. Eur. J. 2011, 17, 3406–3419. doi:10.1002/
chem.201002869
(12) Mateo, C.; Pe´rez-Melero, C.; Peláez, R.; Medarde, M.J.
Org. Chem. 2005, 70, 6544–6547. doi:10.1021/
jo0508393
(13) Mirza-Aghayan, M.; Darabi, H.R.; Ali-Saraie, L.;
Ghassemzadeh, M.; Bolourtchian, M.; Jalali-Heravi, M.;
Neumüller, B. Z. Anorg. Allg. Chem. 2002, 628, 681–684.
doi:10.1002/1521-3749(200203)628:3<681::AID-
ZAAC681>3.0.CO;2-T
(14) Darabi, H.R.; Mirza-Aghayan, M.; Ali-Saraie, L.;
Bolourtchian, M.; Neumueller, B.; Ghassemzadeh, M.
Supramol. Chem. 2003, 15, 55–58. doi:10.1080/
1061027021000003403
(15) Darabi, H.R.; A. Mohebbi, R.; Bolourtchian, M. Supramol.
Chem. 2003, 15, 465–468. doi:10.1080/10610270
310001599195
(16) Darabi, H.R.; Jadidi, K.; Mohebbi, A.R.; Faraji, L.;
Aghapoor, K.; Shahbazian, S.; Azimzadeh Arani, M.;
Nasseri, S.M. Supramol. Chem. 2008, 20, 327–333.
doi:10.1080/10610270701258642
(dd, J = 8.6, 2.5 Hz, 2H), 7.33 (d, J = 2.5 Hz, 2H), 7.16 (dd,
J = 7.5, 1.5 Hz, 4H), 7.00 (d, J = 8.7 Hz, 2H), 6.99 (t,
J = 8.7, 2H), 6.67 (dd, J = 8.7, 1.2 Hz, 2H), 6.60 (s, 2H),
1
5.59 (s, 2H), 4.66 (s, 4H); H NMR (300 MHz, DMSO-d6:
CDCl3 [1:9]): 7.34 (dd, J = 8.6, 2.5 Hz, 2H), 7.26–7.27
(m,2H), 7.05–7.10 (m, 4H), 6.95 (d, J = 8.7 Hz, 2H),
6.80–6.83 (m, 2H), 6.62–6.60 (m, 2H), 6.53 (s, 2H), 5.53
(s, 2H), 4.60 (s, 4H); 13C NMR (75 MHz, CDCl3): 155.6,
154.3, 133.4, 132.2, 131.1, 130.6, 128.4, 128.2, 127.1,
121.2, 119.5, 116.4, 114.3, 95.5, 65.4; HRMS, m/z (rel.
Intensity %) Calculated: 593.99 (M+); found: 593.0143
(M+ nH), 614.9966 (M+ nNa).
Compound E-1d. Colorless solid, mp = 170 ºC; 1H NMR
(500 MHz, CDCl3) δ 7.46 (d, J = 2.5 Hz, 2H), 7.37 (dd,
J = 8.7, 2.4 Hz, 4H), 7.27 – 7.20 (m, 2H), 7.07 (s, 2H), 7.04
– 6.95(m, 6H), 5.73 (s, 2H), 4.97 (s, 4H). 1H NMR (300 MHz,
DMSO-d6) δ 7.69 (d, J = 2.5 Hz, 2H), 7.63 – 7.40 (m, 4H),
7.28 (s, 2H), 7.22 (dd, J = 3.8, 1.0 Hz, 4H), 7.14 (d, J = 8.8 Hz,
2H), 6.92 (m, 2H), 5.97 (s, 2H), 5.01 (s, 4H).13C-NMR
(75 MHz, DMSO-d6): 156.7, 155.4, 134.3, 133.0, 129.23,
129.23, 129.1, 128.3, 128, 128, 121.7, 117.5, 115.2, 114,
93.1, 67.3.; HRMS, m/z (rel. Intensity %) Calculated: 593.99
(M+); found: 593.0143 (M + nH), 614.9966 (M + nNa).
(17) Darabi, H.R.; Azimzadeh Arani, M.; Motamedi, A.; Firouzi,
R.; Herges, R.; Mohebbi, A.R.; Nasseri, S.; Naether, C.
Supramol. Chem. 2009, 21, 632–637. doi:10.1080/
10610270802657650
(18) Darabi, H.R.; Darestani Farahani, A.; Hashemi Karouei,
M.; Aghapoor, K.; Firouzi, R.; Herges, R.; Mohebbi, A.R.;
Naether, C. Supramol. Chem. 2012, 24, 653–657.
doi:10.1080/10610278.2012.678359
Acknowledgments
The Ministry of Science, Research and Technology of Iran is
acknowledged for partial financial assistance of this work.
(19) Darabi, H.R.; Mirzakhani, M.; Aghapoor, K.; Jadidi, K.;
Faraji, L.; Sakhaee, N. J. Organometal. Chem. 2013, 740,
131–134. doi:10.1016/j.jorganchem.2013.05.008
Disclosure statement
No potential conflict of interest was reported by the authors.

SUPRAMOLECULAR CHEMISTRY
7
(20) Darabi, H.R.; Mirzakhani, M.; Aghapoor, K. J. Organomet.
Chem. 2015, 786, 10–13. doi:10.1016/j.jorganchem.
2015.02.047
(21) Izatt, R.M.; Pawlak, K.; Bradshaw, J.S.; Bruening, R.L.
Chem. Rev. 1991, 91, 1721–2085. doi:10.1021/cr00008
a003
(22) Taylor, I.F.; Amma, E.L. Acta Crystallogr. B. 1975, 31,
598–600. doi:10.1107/S0567740875003330
(23) McMurry, J.E.; Haley, G.J.; Matz, J.R.; Clardy, J.C.; Mitchell,
J. J. Am. Chem. Soc. 1986, 108, 515–516. doi:10.1021/
ja00263a032
refinement was carried out with SHELXL using the
X-STEP32 crystallographic software package [X-STEP32
Version 1.07b, Crystallographic Package; Stoe & Cie GmbH:
Darmstadt, Germany, 2000]. The non-hydrogen atoms
were refined anisotropically by full matrix least-squares on
F2 values to final R1 = 0.0640, wR2 = 0.1633 and S = 0.805
with 316 parameters using 4292 independent reflection (θ
range = 2.26-25º). Hydrogen atoms were added in idealized
positions. The crystallographic information file has been
deposited with the Cambridge Data Centre, CCDC
1556553.
(24) Novotney, J.L.; Dichtel, W.R. ACS Macro Lett. 2013, 2,
423–426. doi:10.1021/mz4000249
(25) Bunz, U.H.F.;. Macromol. Rapid Commun. 2009, 30,
772–805. doi:10.1002/marc.200800775
(26) Tyler McQuade, D.; Pullen, A.E.; Swager, T.M. Chem. Rev.
2000, 100, 2537–2574.
(27) X-ray data for Z1d: C29H22Br2O4, M = 594.27, monoclinic
system, space group P21/c, a = 13.179(3) A, b = 8.5689(17), c
(28) Since the detection limit using the S/B ratio is regarded
as the most reliable and accurate, the detection limit
for Cu2+ ions using the S/B ratio was determined on the
basis of a plot of the ratio of the intensity versus the
concentration of Cu2+
.
(29) Guidelines for Drinking Water Quality. WHO Guidelines
Values for Chemicals that are of Health Significance in
Drinking Water, 3rd.; WHO press: Geneva, 2008.
(30) Ditchfield, R.;. Mol. Phys. 1974, 27, 789–807.
doi:10.1080/00268977400100711
(31) Klamt, A.; Schurmann, G. J. Chem. Soc. Perkin Trans.
1993, 2, 799–805. doi:10.1039/P29930000799
(32) Neese, F.;. WIREs Comput. Mol. Sci. 2012, 2, 73–78.
doi:10.1002/wcms.81
= 21.900(4) Å; β = 98.70(3)º V = 2444.7(9) Å3, Z = 4, Dcalcd
=
1.615 g cm−3, μ(Mo-Kα)= 3.350 mm−1, crystal dimension of
0.50 × 0.50×0.40 mm. The X-ray diffraction measurement
was made on a STOE IPDS 2T diffractometer with graphite
monochromated Mo-Kα radiation. The structure was solved
by using SHELXS. The Data reduction and structure