A Shape-Persistent Cryptand for Capturing Polycyclic Aromatic Hydrocarbons

Article abstract of DOI:10.1021/acs.joc.6b01115

A shape-persistent cryptand 1, containing two face-to-face oriented electron-deficient 2,4,6-triphenyl-1,3,5-triazine units separated by approximately 7 ?, and bridged by two rigid 1,8-naphthyridine linkers and a pentaethylene oxide loop, is created for c

Full text of DOI:10.1021/acs.joc.6b01115

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Article
A Shape-Persistent Cryptand for Capturing
Polycyclic Aromatic Hydrocarbons (PAHs)
Rui-Feng Zhang, Wen-Jing Hu, Yahu A. Liu, Xiao-Li Zhao, Jiu-Sheng Li, Biao Jiang, and Ke Wen
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01115 • Publication Date (Web): 03 Jun 2016
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A Shape-Persistent Cryptand for Capturing Polycyclic Aromatic
Hydrocarbons (PAHs)
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⊥
RuiꢀFeng Zhang,†, WenꢀJing Hu,† Yahu A. Liu,‡ XiaoꢀLi Zhao,# JiuꢀSheng Li,*†
Biao Jiang*† and Ke Wen*†
†Shanghai Advanced Research Institute, Chinese Academy of Science, Shanghai
201210, P. R. China
‡Medicinal Chemistry, ChemBridge Research Laboratories, San Diego, CA 92127,
USA
#Shanghai Key Laboratory of Green Chemistry and Chemical Processes, and
Department of Chemistry, East China Normal University, Shanghai 200062, P. R.
China
*Corresponding author. Tel: +86ꢀ21ꢀ20608039; Fax: +86ꢀ21ꢀ20325173
Email address: wenk@sari.ac.cn, lijs@sari.ac.cn, jiangb@sari.ac.cn
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Graphical contents
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ABSTRACT:
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A shapeꢀpersistent cryptand 1, containing two faceꢀtoꢀface oriented electronꢀdeficient
2,4,6ꢀtriphenylꢀ1,3,5ꢀtriazine units separated by approximately 7 Å, and bridged by
two rigid 1,8ꢀnaphthyridine linkers and a pentaethyleneoxide loop, is created for
capturing polycyclic aromatic hydrocarbons (PAHs). Cryptand 1 formed 1:1
complexes with PAH guest molecules, such as phenanthrene (6), anthracene (7),
pyrene (8), triphenylene (9) and tetraphene (10). Singleꢀcrystal structure of complex
6⊂1 revealed that 6 was included in the cavity of 1 via faceꢀtoꢀface π···π stacking
interactions. Soaking crystalline 1 in a toluene solution of anthracene resulted in
picking up anthracene from the toluene solution by the crystalline solid of 1.
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INTRODUCTION
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Polycyclic aromatic hydrocarbons (PAHs),1 consisting of fused aromatic rings that do
not contain heteroatoms or carry substituents, are found naturally in oil, coal, and tar,
or produced as byproducts in combustion processes of fossil fuel.2 PAHs are now
believed to be one of the main pollutants and harmful chemical species known on the
earth3 because some of smaller PAHs have been found to be carcinogenic, mutagenic,
and teratogenic.4 Human exposure to PAHs is primarily from consumption of
contaminated food and water, or PAHsꢀcontaining particulates suspended in air. On
the other hand, PAHs are among the most beautiful and fascinating classes of organic
compounds.5,1 Due to their outstanding optical and electronic properties, many
members of PAHs have been widely investigated in potential applications in organic
fieldꢀeffect transistors (OFETs), organic solar cells (OSCs), fluorescence probes, as
well as other optoelectronic devices.6 Therefore, there is great interest in developing
host molecules for PAH binding and detection. Cyclodextrins (CDs),7 calix[n]arene
derivatives,8 cholic acid,9 ExBox,10 and metallocycles11 have been explored as host
molecules for PAHs of various shapes and sizes. Whitlock and coꢀworkers12 outlined
design criteria for the hosts specifically suited for aromatic guests ꢀ Such host
molecules would contain two aromatic walls separated by a rigid spacer at a distance
of approximately 7 Å, permitting favorable πꢀπ interactions between an aromatic
guest molecule and each of the two walls of the receptor cavity. Based on this model,
many tweezersꢀlike molecules with appropriate geometries and functionalities,
capable of binding aromatic guests, have been developed.13
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As an important class of compounds in hostꢀguest chemistry, cryptands are used
to encapsulate large organic guests, such as paraquat derivatives and ammonium salts.
Due to the wellꢀdefined spatial shapes and cavity sizes, cryptands have shown much
higher binding strength towards guest molecules compared to their analogous crown
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ethers.14 Since most of the existing cryptand hosts were designed to bind
electronꢀdeficient guests, cryptands that could be used to selectively bind
electronꢀrich guests, such as PAHs are rare.14a In this report, we described a new
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cryptand
1
which contains two faceꢀtoꢀface oriented electronꢀdeficient
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2,4,6ꢀtriphenylꢀ1,3,5ꢀtriazine aromatic walls separated by a distance of approximately
7 Å, and linked by two rigid 1,8ꢀnaphthyridine bridges and a flexible
pentaethyleneoxide loop, which was intentionally introduced to increase the solubility
of 1 in organic solvents. Also described are the complexation between the cryptand 1
and five electronꢀrich PAHs and soaking the asꢀsynthesized crystalline solid 1 in a
toluene solution of anthracene for 1 to pick up anthracene from the solution.
RESULTS AND DISCUSSION
Our investigation began from the synthesis of 1,8ꢀnaphthyridineꢀbridged cryptand 1
which is outlined in Scheme 1 (details in Supporting Information). Protection two of
the three hydroxyl groups of 4,4',4''ꢀ(1,3,5ꢀtriazineꢀ2,4,6ꢀtriyl)triphenol (2) by
chloro(methoxy)methane resulted in phenol 3, which was reacted with penta(ethylene
glycol)
bistosylate
under
basic
conditions
to
generate
quadruple
methoxymethylꢀprotected compound 4. Deprotection of the four methoxymethyl
protecting groups of 4 afforded the corresponding tetraphenol 5. The [1+2]
macrocyclization reaction of 5 with 2,7ꢀdichloroꢀ1,8ꢀnaphthyridine yielded the
1
desired cryptand 1 which was characterized by H NMR, 13C NMR, HRꢀMS
spectrometry and single crystal Xꢀray diffraction analysis. The crystal structure of 1
(Figure 1) clearly revealed that its sandwichꢀ like structure with the two faceꢀtoꢀface
oriented electronꢀdeficient 2,4,6ꢀtriphenylꢀ1,3,5ꢀtriazine aromatic units were separated
by a distance of approximately 7 Å, which is longer than those of previously reported
trigonal prismatic bicyclocalixaromatics,15 and the triazineꢀwalled cavity was filled by
two molecules of chloroform, the solvent in which the crystals were harvested. In the
solid state, cryptand 1 molecules were packed in layered fashion and formed
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oneꢀdimensional channels (filled by CHCl3) by appropriate aligning the windows of
the cavity of 1 within each layer (Figure 1). The spaces formed between molecules of
1 within each layer were occupied by solvent molecules, cyclohexane.
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OH
MOMO
N
N
OH
N
N
N
N
O
O
3
MOMO
OMOM
MOMCl
CH3CN/K2CO3
Reflux
MOMO
MOMO
N
N
DMF/K2CO3
+
N
N
N
N
TsO
OTs
O
4
O
HO
OH
2
MOMO
O
4
HO
N
N
N
N
N
N
N
N
O
O
O
O
O
Cs2CO3
DMSO
DCM
HCl
HO
HO
+
O
Cl
N
N
Cl
N
N
N
N
N
O
N
N
O
N
HO
5
O
1
Scheme 1. Synthesis of cryptand host 1
Figure 1. Crystal structure of cryptand 1 (top), oneꢀdimensional channels formed by appropriately
aligning the cavities of 1 in the solid state (bottom). Color code: C (gray), N (blue), O (red), Cl
(green). Hydrogen atoms are omitted for clarity.
With synthesized cryptand 1 in hand, the interaction between the cryptand 1 and
five electronꢀrich PAH guests, phenanthrene 6, anthracene 7, pyrene 8, triphenylene 9
and tetraphene 10 (Figure 2), was investigated with 1D and 2D 1H NMR
1
spectroscopies. The H NMR spectrum of an equimolar mixture of 1 and 6 (10 mM)
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in CDCl3 (Figure 3), revealed obvious upfield shifts for Ha, Hb, Hc and Hd (ꢀ0.144,
ꢀ0.035, ꢀ 0.071 and 0.007 ppm) of cryptand 1, and αꢀ, βꢀ and γꢀphenanthrene proton
signals (ꢀ0.179, ꢀ0.138 and ꢀ0.165 ppm) of guest 6. The ω1ꢀ and ω2ꢀ proton signals of
6 also shifted upfield but became indistinguishable, resulting from πꢀdonor/πꢀacceptor
interactions between the electronꢀrich phenanthrene plane and the electronꢀdeficient
2,4,6ꢀtriphenylꢀ1,3,5ꢀtriazine aromatic walls of the host. The proton signals (He and Hf)
of the 1,8ꢀnaphthyridine units and oxyethylene loop in host 1 experienced no obvious
change upon complexation, implying no interaction existed between the outer edges
of the 1,8ꢀnaphthyridine bridges or oxyethylene loop of host 1 and guest 6.
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Figure 2. The structures of the five PAH guests.
Figure 3. 1H NMR spectra (400 MHz, CDCl3, 298 K, c = 10 mM): (a) 6, (b) 1 + 6, (c) 1.
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The 2D NOESY spectrum of an equimolar mixture of 1 and 6 (10 mM) in CDCl3
(Supporting Information, Figure S17) clearly showed the correlations between the
guest phenanthrene protons (α, β and γ) and the aromatic protons (Ha, Hb, Hc and Hd)
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of host 1, providing additional evidence for the formation of a sandwich type complex
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1
6
⊂
1. A Job plot (Supporting Information, Figure S18) based on H NMR data
indicated that 1 and 6 formed a 1:1 complex. The association constant (Ka) of
1
complex 6
⊂
1 in CDCl3 was determined to be (3.9±0.3) × 101 Mꢀ1 by H NMR
1
titration (Supporting Information, Figure S19ꢀS20). Similarly, the 1D and 2D H
NMR spectra of equimolar mixtures of host 1 with the PAH guests 7, 8, 9 or 10 in
CDCl3 (10 mM) displayed the hostꢀguest interactions between host 1 and each of
these guests (Supporting Information, Figure S21, S22, S26, S27, S31, 32, S37, S38),
and the formation of 1:1 complexes of host 1 and each of the PAH guests was
evidenced by Job plots (Supporting Information, Figure S23, S28, S33, S37). The
association constants (Ka) of the complexes between 1 and 7, 8, 9, or 10 in CDCl3
obtained by 1H NMR titration, are listed in Table 1 (Supporting Information, Figure
S24, S25, S29, S30, S34, S35, S40, S41). The PAH
were detected by HR ESIꢀMS spectrometry (1397.4886 and 1397.4881, assigned to
[9
1+H]+ and [10 1+H]+, respectively. (Supporting Information, Figure S36, S42),
but the other complexes, 6 1, 7 1, and 8 1, with lower association constants, were
not detected by HR ESIꢀMS experimentally, possibly due to dissociation of the
⊂1 complexes 9⊂1 and 10⊂1
⊂
⊂
⊂
⊂
⊂
(4.2 ± 0.4) x 101
(1.2 ± 0.1) x 102
(2.2 ± 0.2) x 102
(2.4 ± 0.2) x 102
Table 1. Hostꢀguest complexes between 1 and PAHs 7-10 and their corresponding association
constants (Mꢀ1) determined by 1H NMR titration.
complexes in the gas phase. Fortunately, single crystals of the complex 6⊂1 suitable
for Xꢀray diffraction analysis were harvested by slow evaporation of the complex
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solution in a mixed solvent of chloroform and cyclohexane. Although the low quality
Xꢀray diffraction data set, possibly due to involvement of highly disordered solvent
molecules, failed to allow us to perform high quality refinement, it provided enough
evidence to confirm the structural skeleton, showing 6 is intercalated between the two
electronꢀdeficient 2,4,6ꢀtriphenylꢀ1,3,5ꢀtriazine aromatic walls of 1 (Figure 4). The
complex is stabilized mainly by πꢀdonor/πꢀacceptor interaction between 1 and 6,
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1
consistent with the H NMR data. In the solid state, the complexes were packed in
layers, and oneꢀdimensional channels were formed within each layer by the inherent
cavities of 1 which were filled by guest molecules of 6. The trapped solvent
molecules (CHCl3 and cyclohexane) were squeezed out during the structural
refinement and were determined to have a 1:6:CHCl3:cyclohexane ratio of 1:1:2:0.5
by 1H NMR analysis of the crystalline solid (Supporting Information, Figure S43).
Figure 4. Crystal structure of hostꢀguest complex between cryptand 1 and phenanthrene (6): side
view (top left), top view (top right), oneꢀdimensional channels in the crystal packing filled by 6
(bottom).
As human exposure to PAHs is primarily from polluted environments, we are
interested in using cryptand 1 to absorb PAHs in order to develop potential materials
which can be used to remove environmental PAH pollutants. We envisioned that
crystalline solids of 1 might be used to absorb PAHs via the displacement of the
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chloroform molecules which occupy the oneꢀdimensional channels. To our delight,
the replacement of chloroform molecules in the oneꢀdimensional channels of the
crystalline solids of 1 by anthracene (7) was achieved by soaking crystalline 1 in a
solution of 7 (1.0 mM) in toluene for one day. The crystalline solid of 1 was
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1
characterized by H NMR spectroscopy before and after soaking (the soaked solid 1
1
was thoroughly washed with toluene). The H NMR spectrum of the soaked
crystalline solids of 1 in acetoneꢀd6 indicated that 7 was indeed sequestered by
crystalline 1, chloroform was no longer in the soaked crystalline solids and the ratio
of 1 to 7 was determined to be 5:2 by integration of corresponding peaks in NMR,
with the remaining cavities filled by toluene molecules (Figure 5). Unfortunately, the
soaked solid of 1 was no longer in decent crystalline form, and thus was unsuitable for
Xꢀray diffraction analysis.
Figure 5. 1H NMR spectra (400 MHz, acetoneꢀd6) of: crystalline solid of cryptand 1 with CHCl3
and cyclohexane (bottom), solid of cryptand 1 after soaking in a 1.0 mM solution of 7 in toluene
for 1 day (middle), 7 (top).
CONCLUSION
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In conclusion, we have created a new cryptand 1 which was found to be able to
encapsulate polycyclic aromatic hydrocarbons (PAHs), such as phenanthrene (6),
anthracene (7), pyrene (8), triphenylene (9) and tetraphene (10), by forming 1:1
complexes through faceꢀtoꢀface π···π stacking interactions. Crystalline 1 was able to
sequester anthracene (7) once soaked in a solution of 7 in toluene. Further research of
complexation of PAHs and potential applications is ongoing.
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EXPERIMENTAL SECTION
General: Unless otherwise noted, starting materials were obtained from commercial
1
suppliers and used without further purification. H and 13C NMR spectra were
recorded at 400 MHz (for 2D NMR) or 500 MHz spectrometers with TMS as the
reference. HRMS spectra were recorded on a micrOTOFꢀQ spectrometer (ESI).
Single crystal Xꢀray diffraction data were collected on a Xꢀray diffractometer
equipped with a normal focus Moꢀtarget Xꢀray tube (λ = 0.71073 Å). Data reduction
included absorption corrections by the multiꢀscan method. The structures were solved
by direct methods and refined by fullꢀmatrix leastꢀsquares using SHELXSꢀ97. All
nonꢀhydrogen atoms were refined anisotropically. Hydrogen atoms were added at
their geometrically ideal positions and refined isotropically.
(4,4',4''-(1,3,5-triazine-2,4,6-triyl)triphenol (2): 4ꢀHydroxybenzonitrile (1.19 g,
10.0 mol) was added to trifluoromethanesulfonic acid (8 mL) portionwise over 4 h at
0ꢀ5 °C under nitrogen resulting in a mixture which was stirred at 0ꢀ5 °C for 1 h and
kept at room temperature overnight. Water (10 mL) was added, and the resulting
mixture was neutralized with aqueous NH3H2O solution (28%). The precipitate was
filtered and washed with water to afford 2 (1.0 g, 84%), m. p.
﹥
300 °C. 1H NMR (500
MHz, DMSOꢀd6): δ 10.28 (s, 3H), 8.56 (d, J = 8.5 Hz, 6H), 6.98 (d, J = 8.5 Hz, 6H).
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13C NMR (126 MHz, DMSOꢀd6): δ 170.5, 162.3, 131.1, 127.0, 116.1. HRꢀMS calcd
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for C21H15N3O3H+ [M + H]+ 358.1186, found 358.1193.
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4-(4,6-Bis(p-(methoxymethoxy)phenyl)-1,3,5-triazin-2-yl)phenol (3): To a solution
of 2 (1.02 g, 2.86 mmol) in DMF (40 ml) was added K2CO3 (787.7 mg, 5.7 mmol),
and followed by dropwise addition of a solution of chloromethyl methyl ether (458.9
mg, 5.7 mmol) in DMF (5 mL). The reaction mixture was stirred at room temperature
for 2 h and poured into water (200 mL), and extracted with EtOAc (3 ×100 mL). The
combined organic extracts were washed with brine, dried with anhydrous Na2SO4,
and concentrated to result in a residue which was subjected to column
chromatography (CH3OH/CH2Cl2 = 0.6 : 100) to afford 3 as a white solid（200.0 mg,
16%), m. p 167.6ꢀ168.1°C. 1H NMR (500 MHz, CDCl3): δ 8.68 (m, 12H), 7.20 (d, J =
9.0 Hz, 8H), 6.98 (d, J = 9.0 Hz, 2H), 5.31 (s, 4H), 3.56 (s, 6H); 13C NMR (126 MHz,
DMSOꢀd6): δ 170.8, 170.5, 162.5, 161.0, 131.2, 130.9, 129.5, 126.9, 116.5, 116.1,
94.2, 56.3. HRꢀMS calcd for C25H23N3O5H+ [M + H]+ 446.1710, found 446.1731.
6,6'-(((Oxybis(ethane-2,1-diyl))bis(oxy))bis(4,1-phenylene))bis(2,4-bis(4-(methox
ymethoxy)phenyl)-1,3,5-triazine) (4): A mixture of 3 (1.00 g, 2.25 mmol),
penta(ethylene glycol) bistosylate (620.0 mg, 1.13 mmol), and Cs2CO3 (1.24 g, 8.98
mmol) in acetonitrile (200 mL) was refluxed for 10 h, poured into water (200 mL),
and extracted with EtOAc (3 ×100 mL). The organic extracts were washed with brine,
dried with anhydrous Na2SO4, and concentrated to result in a residue which was
subjected to column chromatography (CH3OH /CH2Cl2 = 1:100) to afford 4 as faint
yellow oil (1.10 g，
90%). 1H NMR (500 MHz, CDCl3): δ 8.68 (m, 12H), 7.19 (d, J =
8.5 Hz, 8H), 7.06 (d, J = 9.0 Hz, 4H), 5.29 (s, 8H), 4.24 (t, J = 4.5 Hz, 4H), 3.92 (t, J
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= 4.5 Hz, 4H), 3.81 – 3.67 (m, 12H), 3.54 (s, 12H). C NMR (126 MHz, CDCl3): δ
170.7, 170.6, 162.3, 160.7, 130.7, 130.6, 130.1, 129.1, 115.9, 114.4, 94.2, 70.9, 70.7,
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69.7, 67.5, 56.2. HRꢀMS calcd for C60H64N6O14H+ [M + H]+ 1093.4553, found
1093.4581.
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4,4',4'',4'''-((((Oxybis(ethane-2,1-diyl))bis(oxy))bis(4,1-phenylene))bis(1,3,5-triazi
ne-6,2,4-triyl))tetraphenol (5): To a solution of 4 (262.1 mg, 0.24 mmol) in a mixed
solvent of CH3OH and CH2Cl2 (5 mL, 4:1, v/v) was added concentrated hydrochloric
acid (5 mL, 37%) resulting in a mixture which was heated at 50
℃ for 5 h. The
reaction mixture was concentrated, and the residue was subjected to column
chromatography (CH3OH/CH2Cl2 = 5 : 100) to afford 5 as a yellow solid (210.0 mg,
96%), m. p. 134.7ꢀ137.2
℃
. 1H NMR (500 MHz, DMSOꢀd6) δ 10.28 (s, 4H), 8.61 (d,
J = 9.0 Hz, 4H), 8.55 (d, J = 8.5 Hz, 8H), 7.15 (d, J = 9.0 Hz, 4H), 6.98 (d, J = 8.5 Hz,
8H), 4.22 (t, J = 4.5 Hz, 4H), 3.80 (t, J = 4.5 Hz, 4H), 3.67 – 3.49 (m, 12H). 13C NMR
(126 MHz, DMSOꢀd6): δ 170.6, 170.3, 162.7, 162.4, 131.1, 130.8, 128.6, 126.9, 116.1,
115.1, 70.4, 70.3, 69.3, 67.9, 49.1. HRꢀMS calcd for C52H48N6O10H+ [M + H]+
917.3505, found 917.3512.
Cryptand 1: A mixture of 5 (100.0 mg, 0.11 mmol), 2,7ꢀdichloroꢀ1,8ꢀnaphthyridine
(43.6 mg, 0.22 mmol)16 and Cs2CO3 (179.2 mg, 0.55 mmol) in DMSO (16 mL) was
heated at 120
℃ for 2 h, poured into water (80 mL), and extracted with CH2Cl2 (3
×60 mL). The combined extracts were washed with brine, dried over anhydrous
Na2SO4, and concentrated to result in a residue which was purified by column
chromatography (CH3OH/ CH2Cl2 =1:100) to afford 1 as a white solid (26.0 mg,
20%), m. p.
﹥300℃
. 1H NMR (500 MHz, CDCl3): δ 8.77 (d, J = 8.5 Hz, 8H), 8.61 (d,
J = 8.5 Hz, 4H), 8.13 (d, J = 8.5 Hz, 4H), 7.30 (d, J = 9.0 Hz, 8H), 7.17 (d, J = 8.5 Hz,
4H), 7.00 (d, J = 8.5 Hz, 4H), 4.22 (t, J = 4.0 Hz, 4H), 3.91 (t, J = 4.5 Hz, 4H), 3.78 ꢀ
3.68 (m, 12H). 13C NMR (126 MHz, CDCl3): δ 170.8, 170.6, 164.9, 162.4, 156.6,
153.9, 139.6, 133.2, 130.7, 130.6, 128.7, 122.7, 116.8, 114.4, 111.3, 71.1, 70.9, 70.8,
69.6, 67.6. HRꢀMS calcd for C68H52N10O10H+ [M + H]+ 1169.3941, found 1169.3960.
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ASSOCIATED CONTENT
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Supporting Information
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Spectroscopic data for new compounds and complexes, titration protocol, Job plots,
determination of the association constants, and Xꢀray crystallographic data of 1 and
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6⊂1 (CIF files). This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
* EꢀMail: lijs@sari.ac.cn (J.ꢀS. Li)
* EꢀMail: jiangb@sari.ac.cn (B. Jiang)
* EꢀMail: wenk@sari.ac.cn (K. Wen)
Notes
The authors declare no competing financial interest.
⊥RuiꢀFeng Zhang, student of University of Chinese Academy of Sciences, Beijing
100039, P. R. China.
ACKNOWLEDGMENTS
This work is supported by the National Natural Science Foundation of China
(21371177) and the “Strategic Priority Research Program” of the Chinese Academy of
Sciences (XDA01020304) for generous financial support..
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