Order from Chaos: Self-Assembly of Nanoprism from a Mixture of Tetratopic Terpyridine-Porphyrin Conformers

Article abstract of DOI:10.1002/cjoc.201900177

Porphyrins have been widely used in the self-assembly of metallo-supramolecules. In this study, we introduced 2,2':6,2"-terpyridine (tpy) into a porphyrin core to synthesize a tetratopic building block with multiple conformers. During the self-assembly with Zn(II), such a mixture of conformers was able to form a discrete nanoprism with all building blocks in one conformation. Detailed characterizations, including NMR, ESI-MS and traveling-wave ion mobility-mass spectrometry (TWIM-MS), all supported the formation of the desired assemblies. AFM and TEM further confirmed the dimensions of assembled nanoprisms. Moreover, the photophysical properties of the ligands and complexes were noticeably different depending upon size and metal ion center.

Full text of DOI:10.1002/cjoc.201900177

self-assembly, supramolecular chemistry, porphyrinoids,
steric hindrance, fluorescence
中
国 化 学
Order from Chaos: Self-Assembly of Nanoprism from a Mixture of
Tetratopic Terpyridine-Porphyrin Conformers†
Alexander Filosa,a Heng Wang,a Wei-Jian Li,b Wenjing Zhang,c Ellie Ngo,a Jonathan E. Piccolo,a Hai-Bo Yang,b
and Xiaopeng Li*,a
a Department of Chemistry, University of South Florida, 4202 Fowler Avenue, Tampa, Florida 33620, United States
b Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University,
3663 N. Zhongshan Road, Shanghai 200062, China
c College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, Henan 450001, China
Cite this paper: Chin. J. Chem. 2019, 37, 1167—1173. DOI: 10.1002/cjoc.201900177
Summary of main observation and conclusion Porphyrins have been widely used in the self-assembly of metallo-supramolecules. In this study, we
introduced 2,2':6,2"-terpyridine (tpy) into a porphyrin core to synthesize a tetratopic building block with multiple conformers. During the self-assembly
with Zn(II), such a mixture of conformers was able to form a discrete nanoprism with all building blocks in one conformation. Detailed characterizations,
including NMR, ESI-MS and traveling-wave ion mobility-mass spectrometry (TWIM-MS), all supported the formation of the desired assemblies. AFM and
TEM further confirmed the dimensions of assembled nanoprisms. Moreover, the photophysical properties of the ligands and complexes were noticeably
different depending upon size and metal ion center.
5,10,15,20-tetrakis(3-([2,2':6',2''-terpyridin]-4'-yl)phenyl)-7H,8H-
porphyrin, which contains multiple conformational isomers. Dur-
Background and Originality Content
Porphyrins are a vibrant class of organic dyes found widely in
ing the self-assembly, all the building blocks were converted into
nature, ranging from the well-studied chlorophyll and heme found
one conformation through coordination to achieve order from
in the cells of plants and red blooded animals to the less known
chaos. Detailed structural characterization confirmed that the
chlorocruoroporphyrin found in annelids.[1] Porphyrins in natural
conformations of building blocks were fixed within the metallo-
systems are as diverse in structure as they are in function. Heme[2]
supramolecular architecture. Further study showed that the pho-
and chlorocruoroporphyrin[3] function as the core of oxygen
tophysical properties of the ligands and complexes were noticea-
transport proteins, which is responsible for transporting oxygen to
bly different depending upon size and metal ion center.
vital systems; while chlorophyll provides necessary electron
transport functions required for photosynthesis. As a result of
millions of years of successive improvement, nature has perfected
the function of porphyrins. In the field of synthetic chemistry,
substitution and modification have been used to elicit specific
functions of porphyrins. Free base porphyrins have been exten-
Results and Discussion
Scheme 1a depicts the synthesis of a tetratopic tpy-porphyrin
ligand (L1) through established methods.[16] Particularly, the por-
phyrin core was synthesized using the Adler-Longo method.[17]
The metalated ligand (L2) was obtained by treating L1 with 5
sively studied in the biomedical fields, e.g., clinical phototherapy
and cancer imaging.[4] Metallo-porphyrins have been applied in
equivalents of zinc acetate in a 19 : 1 solution of chloroform and
sensors,[5] molecular electronics,[6] photovoltaic devices,[7] iono-
methanol followed by chelation with EDTA to remove the excess
phores[8] and catalysts.[9]
amount of Zn(II) attached to the tpy groups. It is worth noting that
a longer version of tetratopic tpy-porphyrin was reported but with
Much work has been done to increase the size, complexity
different synthetic strategy.[18] Our approach is a metal free syn-
and function of porphyrins with the goal of expanding the scope
thesis, which avoids the multi-armed defects during Suzuki cou-
of porphyrin chemistry, using conventional covalent bonding and
supramolecular self-assembly. For example, porphyrin tweezers[10]
pling and improves the separation.
NMR results of L1 (Figure 1a, Figures S2—S5) provide evi-
dence supporting the existence of isomers (Scheme 1b), which
come from the steric repulsion of HA-HB and HA-HD during the
rotation of tpy groups along phenyl-porphyrin C—C bond. Figure
2a displays a messy spectrum, especially in the region of δ
8.5—8.7, where the peaks are assigned to HG and HJ on the tpy
group. Such NMR shifts indicate the tpy groups in the tetratopic
ligand are settled in various chemical environments, which are
further supported by at least three distinct sets of HI-HJ correla-
tion signals in 2D-COSY spectra (Figure S5). Furthermore, we uti-
lized traveling wave ion mobility-mass spectrometry (TWIM-MS)[19]
to address the conformers in L1. Figure 2a shows the drift time
distributions obtained from ion mobility separation of ions at m/z
771, which corresponds to the [L1+2H+]2+ species according to the
were constructed through the coordination with metal ions to
control the capture and release of guest molecules. Supramolec-
ular porphyrin boxes[11] and cages[12] with unique photodynamic
properties could be applied to the fields of energy harvesting and
cancer phototherapy. Porphyrin macrocycles[13] and prisms[14]
were able to encapsulate large guest molecules and to achieve
enrichment of specific fullerenes with high selectivity.[14b]
In coordination-driven self-assembly, most of the building
blocks possess rigid geometry with single dominant conformation,
which is able to prevent mismatching of the ligands, such as un-
wanted polymerization during the self-assembly.[15] It is rare to
assemble discrete metallo-supramolecules using building blocks
with multiple conformations. Herein, we report the construction
of a porphyrin nanoprism through self-assembly of Zn(II) with
*E-mail: xiaopengli1@usf.edu
For submission: https://mc.manuscriptcentral.com/cjoc
For articles: https://onlinelibrary.wiley.com/journal/16147065
† Dedicated to the special issue of “Supramolecular Chemistry”.
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Scheme 1 (a) Synthesis of tetratopic tpy-porphyrin ligands L1 and L2. (B) Cartoons for the four conformers of L1 (L1-A to L1-D) with different orienta-
tions of tpy
Figure 1 1H NMR spectra of (aromic region, 400 MHz, 300 K) (a) L1 (in CDCl3), (b) S1 (ca. 1 mg/mL in CD3CN), (c) L2 (in CDCl3), and (d) S2 (ca. 1 mg/mL in
CD3CN) and 2D-DOSY spectra of (500 MHz, CDCl3, 300 K) of (e) S1 and (f) S2 (aromic region). * Representing CHCl3 in the solvent.
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Self-Assembly of Nanoprism
Chin. J. Chem.
isotope patterns (Figure 2b). Four distinct signal peaks at different
drift times (i.e., 2.70, 2.84, 3.05, and 3.32 ms, respectively) are
observed in the spectrum, and correspond to four conformers of
L1 with different collision cross-section areas. Similarly, multiple
sets of tpy proton resonance peaks (Figure 1c, Figures S6—S9) in
1H NMR and multi-distributed signal bands in TWIM-MS (Figure S1)
were also observed in L2, indicating that L2 is also a mixture of
conformers. The energy barrier for the rotation of one arm was
studied by conformational search (Figure S31, detailed method
was summarized in SI), which was calculated as 72.44 kJ·mol–1. It
is higher than the rotational energy of C—C in freely rotating
n-butane (19 kJ·mol–1),[20] but lower than that of conformationally
stabilized 1,1'-bi-2-naphthol (167 kJ·mol–1).[21] Compared to the
reported longer version of tetratopic tpy-porphyrin ligand, our
design introduced more restriction to the rotation of tpy with a
short arm, and constructed more compact structures with higher
stability.[18]
theoretical ones based upon the chemical composition of S1 (Fig-
ure 4a inset, Figure S24). We therefore proposed a supramolecu-
lar nanoprism with the simulated structure shown in Figures 3c
and 3d. The possi- bility of forming the Zn-porphyrin (Zn-Por) com-
plexes during the self-assembly of S1 can be excluded by carefully
controlling the amount of Zn(II). The undesired complexation does
not occur because of the preference of forming the Zn-tpy complex
rather than Zn-Por complex, even under the heating process, which
was confirmed during our synthesis of L2.
Figure 2 (a) TWIM-MS spectrum of ions at m/z 771 for L1. Ion mobility
separation gave signals at 2.70, 2.84, 3.05, and 3.32 ms, corresponding to
four conformers of [L1+2H+]2+, respectively. (b) Theoretical and experi-
mental isotope patterns of the four separated peaks.
Because of the dynamic nature of those four conformers, it is
almost impossible to separate the conformers using regular col-
umn chromatography. Among the four possible conformers (L1-A
to L1-D, Scheme 1b), L1-A could be the only candidate for con-
structing a discrete structure via coordination-driven self-assem-
bly because of its introverted conformation. As a result, if we
directly assemble the mixture of ligands with the stoichiometric
amount of Zn(II), three circumstances could occur: (i) formation of
polymeric assemblies; (ii) coexistence of discrete supramolecular
architecture together with polymers; and (iii) generation of a pure
discrete structure via conformational transformation from L1-B/
C/D to L1-A during the assembly process.
Figure 3 Self-assembly of (a) supramolecular nanoprism S1 and (b) S2;
representative energy-minimized structures of S1 (c, d) and S2 (e, f) by
molecular modeling.
ESI-MS of S2 (Figure 4b) gave similar results and the corre-
sponding isotope patterns are shown in Figure 4b inset and Figure
S25, suggesting that a similar nanoprism was assembled (Figures 3e
and 3f). In addition, a single band of signal at each charge state with
narrow distribution is displayed in the TWIM-MS spectra of S1 (Fig-
ure 4b) and S2 (Figure 4d), which excludes the existence of isomers
after the self-assembly. These results indicate that all other con-
formers of L1/L2 were converted to the introverted structure dur-
ing the self-assembly process to form a discrete nanoprism struc-
ture (S1/S2).
After performing the assembly in CHCl3/MeOH (V/V = 1/3) at
50 °C for 5 h, the product was precipitated by adding excessive
NH4PF6 in MeOH solution, followed by several washings with wa-
ter. Then the assemblies of S1 and S2 were obtained in high yields
from L1 and L2, respectively (Figures 3a and 3b), for further char-
acterization. ESI-MS spectrum of S1 (Figure 4a) displays one dom-
inant set of peaks with continuous charge states from 6+ to 10+.
The deconvoluted molecular mass of the assembly is 6749.8 Da,
which agrees well with the molecular composition of three ligands,
Then multi-dimensional NMR spectroscopy was utilized to fur-
ther identify the structure and purity of S1 and S2 (Figure 1, Figures
S10—S23). After the self-assembly, the sharp and well-split peaks of
–
six zinc ions, and 12 PF6 as counterions, viz., [(C104H66N16)3Zn6-
(PF6)12]. The experimental isotope patterns are consistent with the
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probably because the protons are located in the lateral faces of the
nanoprism (Figure 3e). Notably, after coordination, the resonance
signal of Ha was split into two sets after self-assembling into S2,
indicating that Ha settled in two different environments, i.e., the
base surface (Ha1) and lateral surface (Ha2) of the prism. The same
characteristic shifts and the splitting of HA after assembly are also
observed in the spectrum of S1.
A controlled self-assembly of L1/Zn(II) at lower temperature
1
(0 °C ) was conducted. The H NMR spectrum (Figure S32a) of the
complexes assembled at lower temperature displays a great num-
ber of undesired peaks in addition to the peaks of S1, which proves
the formation of polymeric assemblies. The mixture was self-cor-
rected to form pure S1 after 3 h of heating at 50 °C (Figure S32b),
owing to the dynamic transition among the L1-A to L1-D at higher
temperature.
After removing the tpy-coordinated Zn(II) ions in S1 and S2 by
mixing the supramolecular solution with EDTA under room tem-
1
perature, the H NMR spectra of the recovered ligands after chro-
matographic purification show exactly the same spectra with those
of L1/L2 before the assemblies. This further indicates that the tran-
sition potentials among the conformers are relatively low and dy-
namic, and thus drive the conformers into adopting the introverted
conformation for forming the thermodynamically controlled nano-
prism structure during the assembly.
Atomic Force Microscopy (AFM) and Transmission Electron
Microscopy (TEM) were used to image individual supramolecular
nanoprism. Individual dots were observed in both TEM and AFM
images of S1 (Figure 5) with a uniform molecular size. In the AFM
images (Figures 5a—5c), the supramolecules are uniformly dis-
tributed. Using the section analysis on AFM, the height of the
supramolecule is ca. 1.9 nm which shows a good correlation with
the energy minimized model (Figure 3c). The AFM and TEM imag-
es of S2 show similar results, which are summarized in Figure S26.
Figure 4 ESI-MS of (a) S1 and (c) S2. Insets are the theoretical and
experimental isotope pattern of the species with 7+ charge state; TWIM-
MS plots (m/z vs. drift time) of (b) S1 and (d) S2.
supramolecules S1 and S2 instead of broad signals of L1 and L2
suggest that a discrete structure rather than polymeric assemblies
is obtained. 2D-DOSY spectra of S1 and S2 (Figures 1e and 1f) dis-
play single narrowly distributed signal bands with diffusion coeffi-
cients (D) around 1.2 × 10–9 m2·s–1 (S1) and 1.0 × 10–9 m2·s–1 (S2),
respectively, further confirming the isomeric purity of the assem-
blies. More detailed analysis of the 1H NMR spectra of L2 and S2, for
instance, shows characteristic downfield shift of Hf (δ ~0.05) and
obvious upfield shift of Hj (δ ~1.0) after coordination, due to the
electron deficiency of Hf and the electron shielding effect of Hj by
the zinc ions,[22] respectively. In addition, the shifts of the protons
on the phenyl spacer after coordination were observed.
Figure 5 (a) AFM image of S1, (b) 3D AFM image of S1, (c) Cross-section
of one randomly selected particle in (a), (d) TEM images of S1, inset:
zoomed-in TEM images of the selected area.
Concentration-dependence of forming S1 and S2 was carefully
studied. 1H NMR spectra of S1 in various concentrations (Figure S27)
show obvious changes by gradually decreasing the concentration.
For instance, the peaks at σ 7.70, 9.19 and 9.30 shown at high con-
centration (5 mg/mL) gradually shrunk by lowering the concentra-
tion. Only one dominant set of peaks is displayed in the diluted
(0.62 mg/mL) sample. Such a concentration-dependent variation
was also observed in ESI-MS spectra (Figure S29), which helps us
The downfield shifts of Ha,c,e (δ 0.2—0.4) were caused by the
electron withdrawing effect from the coordination sites, while the
abnormal electron shielding on Hd (δ ~0.1 towards upfield) is
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Figure 6 UV-Vis absorption spectra for (a) L1 and S1, (b) L2 and S2 (c = 10.0 µmol·L–1, solvent: 1 : 9 CHCl3/CH3CN); (c) emission spectra for L1, L2, S1 and
S2 (λex = 420 nm, c = 10.0 µmol·L–1, solvent: 1 : 9 CHCl3/CH3CN).
further determine all assembled structures. At a higher concentra-
tion (2.5 mg/mL), besides the dominant set of peaks assigned to S1,
another two minor sets of peaks are also clearly observed, which
are ascribed to tetramer (M4, L14Zn8) and pentamer (M5, L15Zn10),
respectively. These two sets of signals gradually shrink and disap-
pear by diluting the sample solution. The experiment shows that S1
is the major structure in diluted solution.
However, no significant change was observed in the concentra-
tion-dependent experiments of S2, which showed one dominant
set of signals in 1H NMR spectra (Figure S28) and in ESI-MS spectra
(Figure S30) under all concentrations. The significant difference in
concentration-dependent behavior of S1 and S2 might come from
the different flexibility of Zn free porphyrin and Zn-Por backbones.
After coordination with Zn, the porphyrin ring backbone becomes
more rigid and restricts any adjustment required to form the larger
membered prisms.
added into a round bottom flask. The mixture was heated under
60 °C , pyrrole (0.52 g, 7.8 mmol) was added to the mixture, then
the mixture was heated at 145 °C for 3.5 h and cooled to room
temperature. A 4 : 1 mixture of acetone and aqueous ammonia
solution was added, and the flask was kept in a freezer overnight.
The resultant precipitate was collected and washed with cold
methanol 3 times. After being dried, the solid was further purified
by chromatography on SiO2 column with CHCl3 as the eluent. 135
1
mg purple solid was obtained with a yield of 6%. H NMR (400
MHz, CDCl3) δ: 9.00 (s, 16H, HA,F), 8.85 (s, 4H, HD), 8.69—8.54 (m,
8H, HG,J), 8.39—8.31 (m, 8H, HB,E), 7.95 (t, J = 7.9 Hz, 4H, HC), 7.85
(t, J = 8.5 Hz, 8H, HH), 7.3 (t, J = 7.2 Hz, 8H, HI), −2.60 (s, 2H, HK).
13C NMR (100 MHz, CDCl3) δ: 159.16, 156.15, 156.08, 150.17,
149.06, 142.95, 137.01, 136.71, 135.10, 133.18, 127.33, 126.76,
123.69, 121.25, 119.77, 119.31. ESI-MS (m/z): Calculated for
[C104H66N16+2H]2+: 770.2906; found 770.2773.
L2: L1 (61.7 mg, 0.040 mmol) and Zn(OAc)26H2O (59.6 mg, 0.2
mmol) were dissolved in a mixture of 19 mL CHCl3 and 1 mL
methanol, and the resultant mixture was heated for 5 h at 60 °C .
The solvent was evaporated, and the residue was dissolved in
DMF (20 mL). EDTA (59.6 mg, 0.16 mmol) was added into the
DMF solution, and the mixture was stirred at room temperature
for 2 d. The mixture was suspended in water and extracted by
using CHCl3. The organic phases were combined and evaporated.
The residue was further purified by washing with cold acetone.
Absorption and emission spectra of the ligands and supra-
molecules were collected in CHCl3/CH3CN (V/V = 1/9) mixed sol-
vent for all ligands and supramolecules (Figure 6). The absorption
spectra show a strong absorption band at around 420 nm, corre-
sponding to the Soret bands of the porphyrinyl group. The indica-
tive four Q bands are displayed in the UV-Vis of L1 and S1, respec-
tively, around 500—700 nm.[23] In the case of L2 and S2, when
Zn(II) is inserted into the porphyrin ring, the UV-Vis spectra exhib-
it two peaks instead of four in the Q regions, due to the modifica-
tion in the symmetry of the substituted porphyrin ring from D2h of
L1/S1 to the D4h of L2/S2.[23] Two emission bands at 650 nm and
720 nm for L1/S1 and 600 nm and 650 nm for L2/S2 are observed
in the emission spectra (Figure 6c). Obvious weaker emission
spectra are shown in L2/S2 compared with those of L1/S1, due to
the additional zinc atom in the center of the emissive porphyrinyl
chromophore.
1
22.5 mg purple solid was obtained with a yield of 35%. H NMR
(400 MHz, CDCl3) δ: 9.05 (s, 8H, Hf), 8.95 (s, 8H, Ha), 8.85 (s, 4H,
Hd), 8.69—8.52 (m, 8H, Hg,j), 8.40—8.30 (m, 8H, Hb,e), 7.95 (t, J =
7.9 Hz, 4H, Hc), 7.85 (t, J = 9.7 Hz, 8H, Hh), 7.3 (t, J = 7.2 Hz, 8H, Hi).
13C NMR (125 MHz, CDCl3) δ: 156.15, 156.06, 156.01, 155.94,
150.32, 150.26, 149.01, 148.96, 143.79, 136.82, 136.77, 136.72,
136.68, 135.08, 132.98, 132.15, 127.17, 126.45, 123.76, 123.70,
123.64, 121.35, 121.30, 121.25, 120.53, 119.35, 119.30. ESI-MS
(m/z): Calculated for [C104H64N16Zn+2H]2+: 801.7474; found:
801.7339.
Conclusions
S1: L1 (3.0 mg, 1.9 μmol) was dissolved in 4 mL MeOH/CHCl3
(3/1, V/V) solvent, and Zn(NO3)2·6H2O (1.2 mg, 3.9 μmol) was
added in the above solution. The mixture was heated at 50 °C for
5 h, then precipitated in 10 mL NH4PF6 (80 mg 0.49 mmol) solu-
tion in MeOH. The solid was collected by centrifugation, washed
with fresh methanol and water. After drying, 4.0 mg purple solid
Two new porphyrin-based tetratopic tpy ligands, L1 and L2,
were synthesized and proved to have multiple conformers under
ambient temperature. Discrete supramolecular nanoprisms, S1
and S2, instead of a mixture of polymers, were obtained through
coordination-driven self-assembly from the mixture of conform-
ers. Due to the dynamic transformation among these conformers,
nanoprisms were constructed as the energy favorable structures
by fixing all the ligands in one conformation. Therefore, this study
provides another example of “order-out-of-chaos” through self-
assembly.
1
was obtained with a yield of 93%. H NMR (500 MHz, CD3CN) δ:
9.18 (s, 4H, HF), 9.11 (s, 4H, HF), 9.00 (s, 8H, HA), 8.87 (d, J = 7.7 Hz,
4H, HE), 8.69 (s, 4H, HD), 8.57 (d, J = 8.0 Hz, 4H, HB), 8.46 (d, J = 8.0
Hz, 8H, HG), 8.31 (t, J = 7.7 Hz, 4H, HC), 7.62—7.51 (m, 16H, HJ,H),
6.78 (dd, J = 7.7, 5.3 Hz, 8H, HI), –2.75 (s, 2H, HK). 13C NMR (126
MHz, CD3CN) δ: 157.21, 149.90, 148.11, 147.93, 143.42, 141.08,
136.09, 135.81, 128.81, 127.90, 127.43, 123.46, 122.85, 120.18.
ESI-MS (m/z): 979.72 *M−6PF6¯]6+ (calcd m/z: 979.68), 818.87
Experimental
L1: P3 (2.19 g, 6.5 mmol) and propionic acid (20 mL) were
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Comprehensive Report
*M−7PF6¯]7+ (calcd m/z: 818.87), 698.25 *M−8PF6¯]8+ (calcd m/z:
698.27), 604.55 *M−9PF6¯]9+ (calcd m/z: 604.58), 529.59
*M−10PF6¯]10+ (calcd m/z: 529.62).
2018, 28, 1803629; (b) Aoki, T.; Sakai, H.; Ohkubo, K.; Sakanoue, T.;
Takenobu, T.; Fukuzumi, S.; Hasobe, T. Ultrafast Photoinduced Elec-
tron Transfer in Face-to-Face Charge-Transfer π-Complexes of Planar
Porphyrins and Hexaazatriphenylene Derivatives. Chem. Sci. 2015, 6,
1498–1509; (c) Cho, T. J.; Shreiner, C. D.; Hwang, S.-H.; Moorefield, C.
N.; Courneya, B.; Godínez, L. A.; Manríquez, J.; Jeong, K.-U.; Cheng, S.
Z. D.; Newkome, G. R. 5,10,15,20-Tetrakis [4'-(Terpyridinyl)phenyl]-
porphyrin and Its Ru(II) Complexes: Synthesis, Photovoltaic Proper-
ties, and Self-assembled Morphology. Chem. Commun. 2007, 4456–
4458.
S2: L2 (3.1 mg, 1.9 μmol) was dissolved in 4 mL MeOH/CHCl3
(3/1, V/V) solvent, and Zn(NO3)2·6H2O (1.1 mg, 3.8 μmol) was
added in the above solution. The mixture was heated at 50 °C for
5 h, then precipitated in 10 mL NH4PF6 (80 mg 0.49 mmol) solu-
tion in MeOH. The solid was collected by centrifugation, washed
with fresh methanol and water. After drying, 3.9 mg purple solid
1
was obtained, with a yield of 89%. H NMR (500 MHz, CD3CN) δ:
9.03 (s, 4H, Hf), 9.01 (s, 4H, Hf), 8.91 (s, 8H, Ha), 8.73 (d, J = 7.6 Hz,
4H, He), 8.55 (s, 4H, Hd), 8.44 (d, J = 7.9 Hz, 4H, Hb), 8.37 (d, J = 8.1
Hz, 8H, Hg), 8.17 (t, J = 7.7 Hz, 4H, Hc), 7.59—7.48 (m, 16H, Hj,h),
7.59—7.48 (m, 16H, Hj,h), 6.70 (dd, J = 7.9, 5.1 Hz, 8H, Hi). 13C NMR
(125 MHz, CD3CN) δ: 156.99, 150.47, 149.89, 149.52, 147.73,
147.60, 144.32, 140.71, 135.83, 135.41, 135.15, 132.50, 132.10,
128.09, 127.05, 123.08, 122.70, 122.50, 120.14. ESI-MS (m/z):
846.08 *M−7PF6¯]7+ (calcd m/z: 816.12), 722.18 *M−8PF6¯]8+ (calcd
m/z: 722.23), 626.04 *M−9PF6¯]9+ (calcd m/z: 625.99), 548.63
*M−10PF6¯]10+ (calcd m/z: 548.59), 485.57 *M−11PF6¯]11+ (calcd
m/z: 485.54).
[7] (a) Bedioui, F.; Devynck, J.; Bied-Charreton, C. Immobilization of
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Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.201900177.
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Acknowledgement
We gratefully acknowledge the support from the National
Science Foundation (CHE-1506722) and National Institutes of
Health (R01GM128037).
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Manuscript received: April 28, 2019
Manuscript revised: July 24, 2019
Manuscript accepted: August 28, 2019
Accepted manuscript online: August 30, 2019
Version of record online: October 4, 2019
Chin. J. Chem. 2019, 37, 1167－1173
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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