Synthesis of a naphthalene-diimide cyclophane for tuning supramolecular interactions by metal ions

Article abstract of DOI:10.1002/ejoc.201200169

A new supramolecular species of naphthalene-diimide cyclophane containing triazole units was synthesized, and its fluorescent responses to metal ions were investigated in dichloromethane (DCM). The fluorescence emission of NDI was quenched by intramolecular electron transfer, whereas the appearance of dimer emission of the naphthalene-diimide in the presence of Mg²⁺, Ba ²⁺, Hg²⁺, Ca²⁺, Zn²⁺ and Pb ²⁺ was observed. A new naphthalene-diimide cyclophane was synthesized, and the tuning of photoinduced electronic transfer in this cyclophane by metal ions was investigated. Monomer or dimer emission of naphthalenetetracarboxdiimide (NDI) was observed in the presence of different divalent metal ions. Copyright

Full text of DOI:10.1002/ejoc.201200169

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FULL PAPER
DOI: 10.1002/ejoc.201200169
Synthesis of a Naphthalene-diimide Cyclophane for Tuning Supramolecular
Interactions by Metal Ions
Yanwen Yu,[a,b] Yongjun Li,*[a] Songhua Chen,[a,b] Taifeng Liu,[a,b] Zhihong Qin,[a,b]
Huibiao Liu,[a] and Yuliang Li*[a]
Keywords: Click reaction / Triazole / Naphthalene diimide / Cyclophanes / Fluorescence / Electron transfer
A new supramolecular species of naphthalene-diimide cy- was quenched by intramolecular electron transfer, whereas
clophane containing triazole units was synthesized, and its
fluorescent responses to metal ions were investigated in
dichloromethane (DCM). The fluorescence emission of NDI
the appearance of dimer emission of the naphthalene-
diimide in the presence of Mg2+, Ba2+, Hg2+, Ca2+, Zn2+ and
Pb2+ was observed.
chemistry.[11] 1,4,5,8-Naphthalenetetracarboxdiimide (NDI)
derivatives possess an excellent π-conjugated system, low
LUMO energy level and good molecular coplanar proper-
ties. These properties have proven useful for electronic ex-
change and transfer, and have been widely used in many
fields, such as in solar cells,[12] photoconductors, electro-
luminescence, n-type organic semiconductors,[13] anion de-
tection,[14] gas-storage materials,[15] molecular mechanical
machines,[16] targeting specific DNA sequences[17] for pur-
poses of cancer therapy and antibiotic development, and so
on. Triazoles are new motifs that can participate in multiple
noncovalent interactions such as metal coordination,[18]
anion recognition[19] within flexible[20] and shape-persistent
triazolophanes[21] and in foldamers,[22] and they can also
assist in self-assembly.[23] An application of increasing im-
portance is the use of triazoles as electron donors due to
their ability to selectively form complexes, which can
sharply change spectral properties. By using such molecules
that combine different receptor units such as π-conjugated
systems and crown ethers not only expands the function-
ality of the system, but also provides a means to control
physical properties.
Introduction
Recently, great effort has been devoted to the design and
synthesis of photo- and electroactive organic materials.[1]
The design of novel organic molecules containing electron
donors and acceptors constitutes a promising field because
of the unique photoelectronic properties they can instill to
donor–acceptor interactions. Efforts to understand electron
transfer (ET) and/or charge transfer (CT) in these materials
have attracted much attention over the past few decades[2]
and have enabled the design of high-performance molecular
materials. Such efforts have also led to the discovery of new
applications of these systems, such as in molecular elec-
tronic devices,[3] nonlinear optical devices[4] and artificial
photosynthetic systems.[5] A classic model system of intra-
molecular electron transfer is comprised of an electron do-
nor (D) and an electron acceptor (A) connected by some
molecular bridge (B).[6] The number and variety of such
donor–bridge–acceptor (DBA) systems have grown explos-
ively in recent years. Linkers for the D and A elements of
[7]
these systems have been π-bond-conjugated bridges,
σ-
bond bridges, and even hybrid-bond bridges.[8]
There has also been intense interest in the development
of macrocycles by virtue of their high significance in areas
as diverse as drug development[9] and supramolecular
chemistry,[10] which can also be widely used for studies of
catenanes, rotaxanes and transition-metal coordination
In this work, we have designed and synthesized a new
symmetric, and highly rigid, molecule containing the cyclic
NDI dyad, in which triazole donor and NDI acceptor are
linked by short alkyl units. Besides serving as the electron
donor, the triazole can function also as a potential binding
site for metal ions. The tuning of the photoinduced electron
transfer in this cyclophane was also performed with the
[a] Beijing National Laboratory for Molecular Sciences (BNLMS),
CAS Key Laboratory of Organic Solids, Institute of Chemistry,
Chinese Academy of Sciences,
help of metal ions. Divalent metal ions such as Mg2+, Ba2+
,
Hg2+, Ca2+, Zn2+ and Pb2+ can turn off the intramolecular
electron transfer from triazole to NDI by coordinating with
the carbonyl oxygen and triazole nitrogen moieties, fol-
lowed by turning on the electron transfer between the NDI
units, which leads to an enhanced dimer emission of the
NDI.
Beijing 100190, P. R. China
E-mail: ylli@iccas.ac.cn
liyj@iccas.ac.cn
[b] Graduate University of the Chinese Academy of Sciences,
Beijing 100049, P. R. China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201200169.
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Y. Yu, Y. Li, S. Chen, T. Liu, Z. Qin, H. Liu, Y. Li
FULL PAPER
Steady-state optical properties of 6 were investigated,
which showed no solvent effects. The UV/Vis absorption
Results and Discussion
The synthesis of compound 6 from commercially available spectrum of compound 6 in DCM was characterized by a
compounds is illustrated in Scheme 1. A solution of 1 dis- very intense band centered at ca. 358 nm (ε
=
solved in water containing 3 equiv. of sodium azide, which 42000 m–1 cm–1) and 380 nm (ε = 44000 m–1 cm–1), which
was refluxed overnight, afforded the desired amine 2[24] in were assigned to the πǞπ* transition of the aromatic π-
89.5% yield as a colorless volatile oil. Compound 3 and conjugated system in the molecule (Table 1, Figure 1a,
2.2 equiv. of 2 were combined and stirred in DMF at 75 °C black line). The addition of 15 equiv. of metal ions (Mg2+
,
overnight to yield diazide product 4[25] as an analytically Hg2+, Ba2+, Zn2+, Ca2+, Co2+, Cs+, Fe3+, K+, Mn2+, Na+,
pure powder in 81.0% yield. Reaction of 3 with excess 2- Ni2+, Cu2+, Pb2+ as perchlorate salts) (2ϫ10–2 m) in aceto-
propyn-1-amine under similar conditions afforded a 65.0% nitrile to 2 mL solutions of 6 (2ϫ10–5 m) in DCM substan-
yield of dialkyne product 5[26] in only 7 h. We envisioned tially altered the UV/Vis spectra for 6 (2ϫ10–5 m, 2 mL).
the synthesis of 6 to be heavily influenced by concentration The presence of monovalent metal ions (Cs+, K+, Na+)
and to be favored by dilute conditions. Accordingly, a mix- failed to influence the UV/Vis spectra of 6. Alternatively,
ture of 4 and 5 in toluene was added dropwise to a stirred the UV/Vis spectra of 6 displayed 5–14 nm redshifts with
solution of CuI (0.1 equiv.) and DBU (0.05 equiv.) dissolved bivalent and trivalent metal ions. The titration of 6 with
in a large volume of toluene under an inert gas at 75 °C various quantities of Mg2+, Ba2+, Hg2+, Ca2+ and Zn2+
over the course of 2 d. After another 3 d, TLC analysis indi- were performed (Supporting Information Figures S1–S4).
cated that the reaction was complete. It is noteworthy that A typical titration plot for Mg2+ is shown in Figure 1b. The
cycloaddition between 6 and the DBU catalyst at high tem- absorption at 358 nm and 380 nm dramatically decreased
perature was found to occur easily.[27] Furthermore, com- with the gradual addition of Mg2+ to a solution of 6, while
pound 6 was obtained as an insoluble solid due to strong a new set of bands centered at 368 (ε = 32000 m–1 cm–1) and
π–π stacking. As a result, we directly applied column 388 nm (ε = 33600 m–1 cm–1) increased prominently with
chromatography by using toluene/DCM/methanol (100:0:0 three isosbestic points at 363, 373 and 383 nm, which
to 0:99:1) as eluent without concentrating the reaction mix- reached the maximum value at 7.5 equiv. of Mg2+. The ac-
ture beforehand. After column chromatography, cy- tual metal (M)/ligand (L) stoichiometry of binding for 6
clophane 6 – resulting from a CuI-catalyzed click reac- and Mg2+ was found to be 1:2 (Supporting Information
tion[28] – was obtained in about 10% yield and charac- Figure S9). This was further supported by the IR results;
terized on the basis of 1H NMR and high-resolution EI IR absorbance of the carbonyl group in the macrocycle
mass spectra.
shifted from 1667 to 1663 cm–1 upon complexation with
Scheme 1. Synthesis scheme for the preparation of compound 6. DMF = N,N-dimethylformamide; DBU = 1,8-diazabicyclo[5.4.0]undec-
7-ene.
Table 1. Photophysical properties and fluorescence lifetime data for the excimer band of 6 and 6 with Mg2+ (15 equiv.).
Absorption[a]
λmax [nm]
ε[a]
Fluorescence[b]
λmax [nm]
Φfl
Lifetimes
τ2 [ns]
[c]
Entry
Sample
[m–1 cm–1]
τ1 [ns]
χ2
1
2
6
358, 380
368, 388
44000
33600
400
480
0.006
0.009
0.2
14.9
4.2
4.2
1.4
1.1
6 and Mg2+
[a] Measured in DCM solution (1.0ϫ10–5 m). [b] Measured in DCM solution (1.0ϫ10–5 m), upon excitation at the absorption maximum.
[c] In DCM, N,N-bis(2-hydroperoxy-2-methoxyethyl)-1,4,5,8-naphthaldiimide (NP-III, Φfl = 0.01 in acetonitrile)[29] as the standard.
2
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Naphthalene-diimide Cyclophane
Mg2+ ion. Moreover, the ESI MS peak at m/z = 206.0 is
consistent with a 1:2 ratio of the 6/Mg2+ complex (Support-
ing Information). The optical properties of 6 and 6 with
Mg2+ (15 equiv.) in DCM at room temperature are listed in
Table 1.
Figure 2. Fluorescence responses of compound 6 (20 μm) in the
presence of 15 equiv. of various metal ions (Mg2+, Hg2+, Ba2+
,
Zn2+, Ca2+, Pb2+, Co2+, Cs+, Fe3+, K+, Mn2+, Na+, Ni2+, Cu2+) in
a DCM/acetonitrile (1000:15, v/v) solution. Excitation wavelength
was 360 nm with 5 nm slit widths.
(1000:15, v/v) solution at room temperature. The result indi-
cated that the fluorescence lifetime ascribed to the dimer
emission band (τ1) was obviously elongated after the ad-
dition of Mg2+. We also tested the fluorescence emission of
6 with various quantities of Ba2+, Hg2+, Ca2+ and Zn2+
,
which showed similar results (Supporting Information, Fig-
ures S1–S8).
Figure 1. (a) UV/Vis absorption spectra of compound 6 (20 μm)
upon addition of 15 equiv. of different metal ions (Mg2+, Hg2+
Ba2+, Zn2+, Ca2+, Co2+, Cs+, Fe3+, K+, Mn2+, Na+, Ni2+, Cu2+
,
,
Pb2+) in a DCM/acetonitrile (1000:15, v/v) solution; (b) UV/Vis
absorption titration spectra of compound 6 (20 μm) with Mg2+ (0,
1, 1.5, 1.75, 2, 2.5, 5, 7.5, 10, 15 equiv.) in a DCM/acetonitrile
(1000:0–15, v/v) solution.
The fluorescence spectra of 6 in the presence of 15 equiv.
of metal ions (Mg2+, Hg2+, Ba2+, Zn2+, Ca2+, Co2+, Cs+,
Fe3+, K+, Mn2+, Na+, Ni2+, Cu2+, Pb2+ as perchlorate salts)
were recorded (Figure 2). The presence of Fe3+, Co2+, Ni2+
and Mn2+ enhanced the NDI emission at 400 nm, whereas
Mg2+, Ba2+, Hg2+, Ca2+, Zn2+ and Pb2+ not only enhanced
the emission at 400 nm but also led to a new excimer band
at 480 nm. The other ions evaluated had little or no impact
on the emission of 6.
A typical fluorescent titration experiment of 6 with Mg2+
is shown in Figure 3. After the addition of 1.5 equiv. of
Mg2+, a new emission at 480 nm appeared. In the presence
of 10 equiv. of Mg2+, the 480 nm emission band reached its
maximum value. The time-resolved fluorescence spectra of
6 with (τ1 = 14.9 ns, τ2 = 4.2 ns) and without Mg2+ (τ1 =
Figure 3. (a) Fluorescence titration spectra of compound 6 (20 μm)
with Mg2+ (0, 1, 1.5, 1.75, 2, 2.5, 5, 7.5, 10, 15 equiv.) in a DCM/
acetonitrile (1000:0–15, v/v) solution. λex = 360 nm with 5 nm slit
widths; (b) Time-resolved fluorescence spectra of 6 (2ϫ10–5 m) in
DCM with and without Mg2+ (15 equiv.) in a DCM/acetonitrile
0.2 ns, τ2 = 4.2 ns) were recorded in a DCM/acetonitrile (1000:15, v/v) solution at room temp., λex = 360 nm.
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Y. Yu, Y. Li, S. Chen, T. Liu, Z. Qin, H. Liu, Y. Li
FULL PAPER
Time-dependent absorbance (λmax = 388 nm) and fluo- triazole units is weakened, which leads to a slight enhance-
rescence emission (λmax = 480 nm) spectra of 6 and ment of the emission of the NDI moiety (Figure 5, left).
15 equiv. of Mg2+ have been measured within 3 d, indicat- However, for the complex of 6 with Mg2+, the largest coeffi-
ing the stability of the system (Supporting Information, cients in the HOMO and the LUMO are both principally
Figures S10 and S11).
contributed by the NDI moiety, which supports the slight
To gain more insight into the electron-transfer processes redshift of the UV/Vis absorptions in the ground state and
tuned by metal ions in this naphthalene-diimide cy- the appearance of the dimer emission of NDI (Figure 5,
clophane, DFT calculations of the molecular orbitals of 6 right).
with and without metal ions were performed at the B3LYP/
6-31G level by using the Gaussian 03 program.[30] The
HOMO and LUMO orbitals from the calculation are de-
picted in Figure 4.
Conclusions
We have synthesized a new NDI cyclophane and investi-
gated the influence of metal ions on photoinduced electron
transfer in this donor–bridge–acceptor system. This new
scaffold enables: (i) the turning off of the photoinduced
electron transfer from the triazole to the NDI moieties by
divalent metal ions such as Mg2+, Ba2+, Hg2+, Ca2+, Zn2+
and Pb2+, (ii) the turning on of the electron transfer be-
tween the NDI units at the same time, which leads to an
enhanced dimer emission of the NDI. However, Fe3+, Co2+
,
Ni2+ and Mn2+ were found to only enhance the monomer
emission of NDI. Such supramolecular systems are the ba-
sis for molecular electronic devices that can be potentially
applied as optical switches, sensors and artificial photosyn-
thetic systems.
Experimental Section
1
General Methods: H and 13C NMR spectra were obtained with a
Bruker ARX400 spectrometer by using tetramethylsilane (TMS) as
the internal standard, and chemical shifts (δ) are given in ppm rela-
tive to TMS. Matrix-assisted laser desorption/ionization reflectron
time-of-flight (MALDI-TOF) mass spectrometry was performed
with a Bruker Biflex III mass spectrometer. Elemental analyses
were carried out with a Carlo Erba 1106 elemental analyzer. Melt-
ing points were obtained from TGA data recorded by using a
DTG-60 SHIMADZU apparatus. Electronic absorption spectra
were measured with a JASCO V-579 spectrophotometer. Fluores-
cence excitation and emission spectra were recorded by using a Hit-
achi F-4500 instrument. The fluorescence decay curves were deter-
mined by using an Edinburgh FLS-920 instrument with single-pho-
ton counting measurement. Accordingly, samples were irradiated
Figure 4. HOMO orbitals (left) and LUMO orbitals (right) of 6
(a), 6 after addition of Ni2+ (b) and 6 after addition of Mg2+ (c)
obtained by using DFT calculations at the B3LYP/6-31G level.
For cyclophane 6 itself, the density in the HOMO is con-
centrated in the triazole moiety, while the density in the
LUMO is mainly localized on the two NDI planes. It is
expected that electron transfer from the triazole moieties to
the NDI planes should lead to a weak emission of NDI
(Figure 5, center). In the presence of Ni2+, the largest coeffi- with a Picoquant LDH-D-C-375 pulsed diode laser.
cients in the HOMO are mainly localized on the NDI moi-
Materials: Synthesis of 6 employed chemicals and solvents that
were reagent grade purchased from Aldrich, ACROS Chemical Co.,
and used without further purification. The silica gel (200–
ety, and the largest coefficients in the LUMO are mostly
contributed by the two triazole units coordinated to Ni2+
.
The results indicate that the electron-donating ability of the 300 mesh) for column chromatography was purchased from JI-
YIDA Silica Gel Corp. in Qing Dao.
Spectroscopy Measurement: Solutions of compound 6 (2ϫ10–5 m)
were prepared with DCM (HPLC grade). The UV/Vis absorption
spectra of compound 6 before and after addition of metal ions at
room temp. in solution were measured; fluorescence emission spec-
tra were measured with excitation at 360 nm. The fluorescence life-
times of compound 6 before and after addition of 15 equiv. of Mg2+
were measured at room temp. in solution under deaerated condi-
tions.
3-Azido-1-propylamine (2): To
a stirred solution of 1 (5 g,
22.8 mmol) dissolved in water (16 mL) was added aqueous sodium
azide (4.45 g, 68.5 mmol in 10 mL of water), and the mixture
Figure 5. Schematic interpretation of the electron-transfer process
tuned by metal ions.
4
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Naphthalene-diimide Cyclophane
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dried with MgSO4 and concentrated to give the desired amine 2 as
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N,NЈ-Bis(3-azidopropyl)-1,4,5,8-naphthalenetetracarboxdiimide (4):
Compound 3 (2.14 g, 8.0 mmol) and 2 (2.2 equiv.) were combined
in DMF (40 mL). The mixture was stirred at 75 °C overnight. The
resulting precipitate was filtered off, rinsed with acetone, and dried
in a vacuum oven to give 4 as an analytically pure powder (2.8 g,
81.0% yield). M.p. 187–188 °C. IR (neat):ν
= 2118 (N3) cm–1.
˜
max
[7]
[8]
[9]
1H NMR (400 MHz, CDCl3): δ = 8.78 (s, 4 H), 4.32 (t, J = 7.04 Hz,
4 H), 3.47 (t, J = 6.60 Hz, 4 H), 2.06 (m, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 163.01, 131.31, 126.92, 126.73, 49.56,
38.67, 27.68 ppm. EI-MS: m/z = 404 [M – N2]. C20H16N8O4
(432.40): calcd. C 55.55, H 3.73, N 25.91; found C 55.27, H 3.65,
N 26.13.
N,NЈ-Bis(prop-2-ynyl)-1,4,5,8-naphthalenetetracarboxdiimide
(5):
[10]
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overnight. The precipitate was filtered out, rinsed with acetone, and
dried in a vacuum oven to give product 5 as an analytically pure
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solution of copper(I) iodide (0.1 equiv.) and DBU (1.36 mL) dis-
solved in toluene (600 mL) under nitrogen was added dropwise a
[12]
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4 (267 mg, 0.617 mmol) and 5 (211 mg,
0.617 mmol) in toluene, while the temperature was kept at 75 °C
for 48 h. After another 3 d, TLC analysis showed that the reaction
was complete. The white solid product 6 (47 mg, 10% yield) was
obtained after direct column chromatography by using toluene/
DCM/methanol (100:0:0 to 0:99:1) as eluent. M.p. Ͼ 300 °C. 1H
NMR (400 MHz, CDCl3): δ = 8.85 (s, 4 H), 7.84 (s, 2 H), 7.71 (s,
4 H), 5.55 (s, 4 H), 4.48 (t, J = 4.00 Hz, 4 H), 3.99 (t, J = 6.48 Hz,
4 H), 2.36 (m, 4 H) ppm. HRMS (EI): calcd. for C40H26N10O8
774.1935; found 774.1945. 13C NMR spectra of 6 were not well
resolved due to poor solubility.
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1
with metal ions, H and 13C NMR spectra for key intermediates,
1H NMR and HR-EI mass spectra of 6.
Acknowledgments
[18]
[19]
We are grateful for financial support from the National Nature
Science Foundation of China (21031006, 20971127) and the
National Basic Research 973 Program of China.
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Y. Yu, Y. Li, S. Chen, T. Liu, Z. Qin, H. Liu, Y. Li
FULL PAPER
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Received: February 23, 2012
Published Online: ᭿
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Date: 18-06-12 11:34:03
Pages: 7
Naphthalene-diimide Cyclophane
Cyclophane-Modulated Electron Transfer
Y. Yu, Y. Li,* S. Chen, T. Liu, Z. Qin,
H. Liu, Y. Li* ................................... 1–7
Synthesis of a Naphthalene-diimide Cyclo-
phane for Tuning Supramolecular Interac-
tions by Metal Ions
Keywords: Click reaction
Naphthalene diimide Cyclophanes
Fluorescence / Electron transfer
/
Triazole
/
/
A
new naphthalene-diimide cyclophane
Monomer or dimer emission of naphth-
alenetetracarboxdiimide (NDI) was ob-
served in the presence of different divalent
metal ions.
/
was synthesized, and the tuning of photo-
induced electronic transfer in this cyclo-
phane by metal ions was investigated.
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