Article

Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX pubs.acs.org/IC

Conventional and Mechanochemical Syntheses of Copper(I) Iodide

Luminescent MOF with Bis(amidoquinoline) and Its Application for
the Detection of Amino Acid in Aqueous Solution
Eunji Lee,† Huiyeong Ju,† Jong Hwa Jung,† Mari Ikeda,‡ Yoichi Habata,*,§ and Shim Sung Lee*,†
†
Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, South Korea
‡
Education Center, Faculty of Engineering, Chiba Institute of Technology, 2-1-1 Shibazono, Narashino, Chiba 275-0023, Japan
§
Department of Chemistry, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan
*
S Supporting Information
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ABSTRACT: Formation of a copper(I) iodide cluster based

luminescent metal−organic frameworks (LMOFs) and its
utilization for the detection of cysteine (Cys) in aqueous
solution are reported. The reaction of bis(amidoquinoline)
ligand (L) with copper(I) iodide afforded an LMOF {[(Cu2I2)
L2]·2DMSO}n (1) with a 44-sql topology linked by Cu2I2
clusters as a thermodynamic product. Time- and temperature-
dependent PXRD experiments confirmed that the entire
formation process for 1 is kinetically and thermodynamically
controlled. Interestingly, LMOF 1 was also obtained under the
mechanochemical condition. Moreover, LMOF 1 dispersed in
water shows a selective quenching for Cys over other amino
acids due to the strong affinity of Cys to copper(I) iodide. On the basis of the NMR data of L isolated from the decomposition
of 1, the decomposition−displacement mechanism was proposed for the sensing of Cys. This result might be utilized for the
practical detection of Cys because the sensing material can be prepared simply, and the sensing process is performed in aqueous
media.

■ INTRODUCTION
Metal−organic frameworks (MOFs) and coordination polymers
(CPs) often exhibit interesting physical properties including gas
storage, magnetism, and luminescence.1−9 In particular, the
luminescent MOFs (LMOFs) provide opportunities to extend
their applications as organic light-emitting diodes, molecular
switches, and chemosensors.6−17 In the past decade, LMOFs
were employed for sensing small organic molecules including
volatile organic compounds (VOCs), explosive nitroaromatic
species, and amino acids.10−19
Beyond their role as residues in proteins, amino acids are
crucially involved in various processes such as neurotransmitter
transport and biosynthesis.20 Thus, detection of amino acids is
essential in the nutritional analysis21 and the diagnosis of
diseases such as Alzheimers22 and pancreatitis.23 In particular,
the sensing of cysteine (Cys) in biological fluids has been a surge
of interest because it is one of the semiessential protein-building
amino acids and a precursor in the pharmaceutical and personal-
care industries.
Among the generally employed analytical techniques,24−27
which include HPLC, luminescent/colorimetric detection,24,25
capillary electrophoresis,26 and electrochemical methods,27 the
fluorescence probe for Cys detection is remarkable because of its
rapid sensing with high sensitivity. Some fluorescent probe for
detection of Cys, utilizing copper(II) complex of bi-8-
carboxamidoquinline,28 hemicyanine dye,29 and iminocoumar-
in30 have been reported. Despite of a wide range of fluorescent
sensors for amino acids, the large portion is carried out in water/
organic mixed media,31,32 which limit their application in
biological system. Therefore, the development of LMOFs for the
detection of Cys in aqueous solution is a challenging task.
Among the LMOFs, polynuclear copper(I) iodide cluster
based coordination networks are particularly attractive because
of their strong photoluminescence (PL) assigned to MLCT with
some mixing of XLCT characters.33−37 The solvatochromic
behaviors of the porous [CunIn]-based LMOFs via guest
exchange and their use in detecting small organic molecules
including VOCs have been introduced.35,38 In spite of the huge
progress on the [CunIn] based LMOFs, the application in amino
acid sensing is still an unexplored area. The reason is probably
that amino acids are nonvolatile and that the access via guest
exchange is difficult in aqueous solution.
Considering the sulfur content in Cys and the thiaphilicity of
copper(I),39 the expected stronger bonding of S−Cu+ over that
of N−Cu+ might serve an opportunity to rationalize a Cys
sensing system as depicted in Scheme 1. In connection with this
reason, we have proposed a formation of [CunIn] cluster based
Received: September 7, 2018

© XXXX American Chemical Society A DOI: 10.1021/acs.inorgchem.8b02549

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Inorganic Chemistry Article

Scheme 1. Cys Sensing (Turn-Off) Using Copper(I) Iodide Cluster based LMOF via Replacement Mechanism

LMOF which might be decomposed to the weak or nonemissive

free ligand via replacement mechanistic process.
On the basis of the above suggestion, we have employed
bis(amidoquinoline) ligand (L, Scheme 2), which might act as a

Scheme 2. Preparation of Copper(I) Iodide Complexes 1 and

2

semiflexible linker via N−Cu+ bonding to afford an LMOF. In

fact, L has been reported by Cain group in 1967 together with a
series of bis quaternary ammonium heterocycles, as potential
antitumor agents.40 Here, we report the preparation of an
emissive 2D copper(I) iodide coordination network with L
which offers an opportunity to explore the detection of Cys via
the naked eye in aqueous solution. To the best of our knowledge,
such amino acids sensing system in water utilizing copper(I)
iodide cluster based LMOF has not yet been documented.

■ RESULTS AND DISCUSSION

Preparation of Copper(I) Iodide Complex (1). Ligand L
was prepared as described previously40 and confirmed by 1H and
13
C NMR since its NMR data have not yet been reported
(Figure S1). It is notable that the reaction of L with CuI in
dichloromethane/acetonitrile yielded two products (1 and 2)
with different photophysical properties depending in reaction
time (Scheme 2). For example, a greenish yellow precipitate
(termed 2) appeared after stirring of the reaction mixture for 1 h,
and continuous stirring for another 24 h under the same
condition afforded an orange emissive solid (termed 1). The Figure 1. (a) PXRD patterns and (b) PL spectra for the solid products
recrystallization of 1 yielded X-ray quality crystals. Powder X-ray isolated from the reaction mixture by varying the reaction times (1−24
diffraction (PXRD) analysis has been performed to monitor the h) at room temperature, showing the PL changes from greenish-yellow
time- and temperature-dependent kinetic and thermodynamic (2) to orange (1) colors.
products.
PXRD and PL Studies. To monitor the influence of reaction and 1. After 12−24 h, the evidence of 2 disappears, and only 1
time on the copper(I) iodide complex formations of L exists. At 50 °C, the same reaction afforded the orange solid of 1
systemically, time-dependent PXRD experiments were per- (Figure S2).
formed by varying the reaction time from 1 to 24 h with stirring The solid-state PL spectra for the products isolated with
at room temperature (Figure 1a). When the reaction times are in different reaction times were obtained at room temperature
the range of 1−5 h, the PXRD patterns of the products (denoted (Figure 1b). Product 1 exhibits a greenish yellow emission at
with greenish-yellow color) were not changed, indicating that 2 560 nm, and the longer reaction times show a gradual redshift of
is the only product in this range. After 7 h, some new peaks the maxima emission. Eventually, the reaction time of 24 h
(denoted with orange reciprocal triangles) appear which exhibits an orange emission at 590 nm indicating the existence of
correspond to 1, indicating the formation of a mixture of 2 product 2 which is likely due to a cluster-centered excited state
B DOI: 10.1021/acs.inorgchem.8b02549
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Inorganic Chemistry Article

Figure 2. Crystal structure of 1, {[(Cu2I2)L2]·2DMSO}n: (a) core coordination unit, (b) view of the 44-sql net of the 2D coordination polymer, (c)
packing with A−B−A−B stacked pattern, and (d) closer view of A and B layers. Non-coordinating solvent molecules are omitted.

with mixed halide-to-metal charge transfer.41−49 From the

combined results of the PXRD, PL, and high-temperature (50
°C) reaction, it is concluded that the conversion of 2 to 1 is in
accord with complex 2 being a kinetic product, with complex 1
being a thermodynamic product.
Crystal Structure of 1. The recrystallization of 1 from
DMSO/diethyl ether yielded single crystals. X-ray analysis
reveals that 1 is a square-grid type 2D coordination polymer of
the formula {[(Cu2I2)L2]·2DMSO}n (Figure 2). The asym-
metric unit contains a half of Cu2I2 cluster and one L ligand.
Each tetrahedral Cu atom in the Cu2I2 cluster is bound to two
iodide atoms and two nitrogen atoms from different L ligands in
a twisted conformation. Accordingly, the Cu2I2 cluster links four
L ligands via Cu−N bond [2.108(3) Å], forming a 2D undulated
net, taking Cu2I2 clusters as 4-connected nodes and the 2D layer
has a 44-sql topology that extends to the ab-plane (Figure 2b).
Figure 3. PL spectra of L and 1 in the solid state at room temperature
Notably, the 2D sheet structure of 1 is highly undulated with a (excitation at 365 nm).
thickness of 14 Å. Thus, the layers in 1 are stacked together in an
A−B−A−B fashion forming a pseudo-3D structure (Figure
2c,d).
PL spectra of L and 1 (Figure 3) and their quantum yields in nm. As mentioned, 1 exhibits an orange emission at 590 nm. The
the solid state were measured at room temperature. Ligand L is absolute quantum yields for L and 1 at 365 nm were determined
emissive in the blue region with the peak centered at λmax = 424 to be Φ = 0.034 and 0.095, respectively.
C DOI: 10.1021/acs.inorgchem.8b02549
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Inorganic Chemistry
In the TGA of complex 1, the weight loss of 11.43% was
observed over 200 °C, corresponding to the removal of two
DMSO molecules in the lattice (calcd 11.37%) (Figure S3).
Then, the curve shows a plateau until 350 °C, indicating the
framework being stable at this temperature. At the higher
temperature, however, the network structure begins to
decompose.
Mechanochemical Preparation of 1. On grinding the
solid mixture of CuI and L in our preliminary work, a significant
PL change was observed under the excitation by a UV lamp
(Figure 4a). On the basis of this observation, we assumed that
Figure 4. (a) Mechanochemical reaction process. (b) Confirmation of
product 1 via the PXRD patterns.
the solvent-assisted mechanochemical reaction between CuI
and L may occur,50,51 so the mechanochemical preparation of
the CuI−L system by manual grinding (30 min) was
accomplished in the presence of several drops of solvents.
Interestingly, complex 1 was also obtained under the
mechanochemical condition in the presence of 3 drops of
CH3CN and 1 drop of DMSO for 30 min, as confirmed by
comparative PXRD patterns (Figure 4b) and the PL spectra
(Figure S4).
PL Sensing for Cysteine (Cys). In order to detect the
organic guest molecules such as pharmaceuticals, carcinogens,
nitro-containing explosives, and amino acids, several types of
LMOFs have been utilized.17,18,28−32 The observed luminescent
nature of 1 encouraged us to investigate the possible detection of
guest molecules. For this reason, the solid particles of 1 prepared
via the conventional process (Scheme 2) were dispersed in water
(average particle size: 1941 nm in 1 mg/1 mL H2O, Figure S5).
Upon excitation of this dispersed aqueous solution at 365 nm, an
orange emission (590 nm) was observed (Figure 5a). To
monitor the PL changes induced by amino acids, the different
amino acid solutions prepared (3 mM) were added to the
D DOI: 10.1021/acs.inorgchem.8b02549
Article
Figure 5. (a) PL spectral changes of 1 (1 mg dispersed in 1 mL H2O) in
the presence of amino acids (3 mM). Inset: photograph of 1 after the
addition of amino acids in water under the UV lamp (365 nm). (b) PL
quenching efficiencies (I0/IQ − 1) obtained from different amino acids
by 1 (I0 and IQ: the emission intensities before and after addition of
amino acids, respectively).
dispersed solution of 1 (1 mg/1 mL H2O). Interestingly, Cys
showed the highest PL quenching efficiency among 12 different
amino acids used (Figure 5). While no significant changes were
observed by addition of other amino acids.
Time-dependent PL spectra of 1 with Cys (3 mM) were
collected in water. In this case, the emission intensity at 590 nm
decreased gradually and minimized after 8 min, indicating the
equilibrium state at this point (Figure S6). Notably, an isosbestic
point was observed at 509 nm as the reaction proceeded. Thus,
all the PL measurements in the control experiments were
performed after 8 min upon addition of each amino acid.
Given the high selective recognition of Cys, the use of 1 was
tested as a “Turn-Off” sensor in aqueous media. Upon addition
of Cys into a solution of 1, the emission intensity at 590 nm
decreases linearly in the range of 0−1200 μM of Cys (inset in
Figure 6), indicating that 1 is suitable for the detection of Cys
quantitatively in the moderate condition.
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Inorganic Chemistry
Figure 6. PL spectra of 1 (1 mg dispersed in 1 mL of H2O) after 8 min
upon addition of Cys (0−1200 μM) in water (λex = 365 nm). Inset: the
emission intensities at 590 nm as a function of [Cys].
Using a Stern−Volmer equation (I0/IQ = 1 + KSV [Cys]) for
the data in Figure 6, the quenching constant (KSV) was obtained.
The Stern−Volmer plot is almost linear at low concentrations
(0−350 μM, Figure S7), suggesting the static quenching process
is predominant in this region. On the basis of the linear part, KSV
is calculated to be 6.128 × 102 M−1 (R = 0.9914). The plot is
deviated from linearity and curves upward at high concentration
range. The luminescence decay experiments revealed that the
average excited-state life times of 1 and 1 + Cys are 1.1 and 0.6
μs, respectively (Figure S8). It is known that the lifetime is
reduced in the presence of the quencher when the dynamic
quenching process is predominant. Overall, the observed
quenching result could be preceded through both static and
dynamic processes.52,53 Control experiments were performed
using alanine (Figure S9).
In order to understand the possible quenching mechanism, an
aqueous solution of 1 in the presence of Cys was monitored. As
shown in Figure 7, 5 equiv of Cys was added to the aqueous
Figure 7. (a) Representation of decomposition-displacement sensing
mechanism. 1H NMR spectra of (b) L, (c) complex 1, and (d)
precipitate isolated from a mixture of 1 and Cys in DMSO-d6.
E DOI: 10.1021/acs.inorgchem.8b02549
Article
disperse solution of 1, the orange emissive color changed to
nonemissive, forming a colorless precipitate. After washing with
dilute aqueous NaOH and drying, the 1H NMR spectrum of the
precipitate in DMSO-d6 was obtained (Figure 7d). By
comparing with the NMR spectra of L (Figure 7b) and 1
(Figure 7c), the precipitate (Figure 7d) was confirmed as a free
form of L which was recovered from the decomposition of 1.
This result suggests that the CuI−Cys complex species could be
more stable than that of the 2D coordination polymer 1 in the
presence of Cys. Indeed, Rigo et al.39 reported NMR titration
data for a 1:1 complexation of Cu+−Cys in aqueous solution
(K1:1 = 7.9 × 109 M−1) which stabilizes by the strong binding of
the thiol group to copper(I). In other words, Cys acts as an
efficient ligand for Cu(I), leading to the decomposition of the
2D network to release L. We also confirmed that the emissive 1
was regenerated when CuI was added to the isolated L solution.
On the basis of these observations, we propose a decom-
position−displacement mechanism54,55 for sensing (Figure 7a).
■ CONCLUSION
In summary, a copper(I) iodide cluster based 2D LMOF 1 with a
44-sql topology was prepared from the assembly reaction with
bis(amidoquinoline) ligand (L). LMOF 1 was also prepared
quantitatively under the mechanochemical condition. LMOF 1
shows a selective PL quenching for Cys compared to other
amino acids in aqueous solution. The observed sensing ability
for Cys appears to be unprecedented and its decomposition−
displacement sensing mechanism is proposed. Despite some
limitations of the LMOF-based sensing system for the practical
use, the observed results could be a meaningful progress for the
amino acid detection because of its reasonable performances
including the simple procedure and reproducible result in
aqueous solution.
■
EXPERIMENTAL SECTION
General. Chemicals and solvents employed in the synthetic works
were reagent-grade and used as received. NMR spectra were obtained
by using a Bruker DRX 300 spectrometer. FT-IR spectra were recorded
on a ThermoFisher Scientific Nicolet iS 10 FT-IR spectrometer.
Thermogravimetric analyses were recorded on a TA Instruments TGA-
Q50 thermogravimetric analyzer. ESI-mass spectra were obtained on a
Thermo Scientific LCQ Fleet spectrometer. The PL spectra were
performed on a RF-5301 spectrophotometer. The absolute quantum
yields were measured with a Hamamatsu Quantaurus-QY C11347−11
absolute PL quantum yields measurement system. The PXRD
experiments were performed in a transmission mode with a Bruker
GADDS diffractometer. The elemental analysis data was obtained by a
Thermo-Fisher Scientific Flash 2000 elemental analyzer.
Preparation of L. Ligand L was prepared via the modified
procedure of the reported method in the literature.40 To a stirred
solution of terephthaloyl chloride (1.00 g, 4.93 mmol) in 50 mL of
dichloromethane in a round-bottomed flask, were added 5-amino-
quinoline (1.47 g, 10.2 mmol) and triethylamine (2.10 g, 20.7 mmol).
The reaction mixture was stirred for 4 h, and the resulting pale-yellow
precipitate was collected by filtration, washed with water, methanol,
acetone, and diethyl ether. The solid product was dried in a vacuum
oven. Yield: 75%. 1H NMR (300 MHz, DMSO-d6): δ 10.78 (s, 2 H,
NH), 8.97−7.57 (m, 16 H, Ar). 13C NMR (75 MHz, DMSO-d6):
166.40, 151.09, 148.67, 135.05, 134.50, 132.63, 131.57, 129.52, 129.27,
128.02, 127.77, 124.66, 124.23, 121.62. IR (KBr pellet): 3247, 3156,
3064, 3035, 3011, 1641, 1596, 1542, 1497, 1480, 1408, 1364, 1330,
1300, 1277, 1250, 1075, 914, 824, 789, 695, 670, 658, 644 cm−1. Mass
spectrum: m/z = 419.25 [C26H19N4O2]+.
Preparation of {[(Cu2I2)(L)2]·2DMSO}n (1). CuI (10.2 mg, 0.053
mmol) in acetonitrile (1 mL) was added to a solution of L (20.1 mg,
0.048 mmol) in dimethyl sulfoxide (DMSO, 1 mL). A greenish-yellow
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
precipitate was obtained after stirring for 1 h. The precipitate was
filtered off, washed with diethyl ether, and dried in air (yield 80%). The
precipitate was dissolved in DMSO and vapor diffusion of diethyl ether
into the DMSO solution yielded X-ray quality crystals. Mp: over 250 °C
(decomp). IR (KBr pellet): ν = 3228, 3057, 2982, 2902, 1667, 1650,
1589, 1540, 1502, 1474, 1411, 1366, 1325, 1302, 1279, 1252, 1209,
1179, 1074, 1040, 955, 805, 703, 661, 644 cm−1. Anal. Calcd for
[C28H24CuIN4O3S]: C 48.95, H 3.52, N 8.15, S 4.67. Found: C 49.06,
H 3.58, N 8.23, S 4.49.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.8b02549.
NMR spectra of L, PXRD patterns, TGA data for 1, PL
spectra, particle size distribution, Stern−Volmer plots
(PDF)
Accession Codes
CCDC 1864198 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_
request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336033.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: habata@chem.sci.toho-u.ac.jp (Y.H.).
*E-mail: sslee@gnu.ac.kr (S.S.L.).
ORCID
Eunji Lee: 0000-0002-3031-943X
Jong Hwa Jung: 0000-0002-8936-2272
Shim Sung Lee: 0000-0002-4638-5466
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by NRF (2016R1A2A205918799 and
2017R1A4A1014595), South Korea. The Support Program for
Strategic Research Foundation at Private Universities
(S1201034) and KAKENHI-PROJECT-17K05844 from the
Ministry of Education, Sports, Science and Technology of Japan
are acknowledged.
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G DOI: 10.1021/acs.inorgchem.8b02549
Inorg. Chem. XXXX, XXX, XXX−XXX