Fabrication and morphology control of the electrostatic self-assembled system containing porphyrin electrolytes and sulfonated fullerene derivatives

Article abstract of DOI:10.1080/10610278.2014.909043

A series of water-soluble porphyrin electrolytes with quaternary ammonium ions side chains (TEMZnPN and THMZnPN) and sulfonated fullerene derivatives were synthesised and characterised. The self-assembled system was fabricated through the electrostatic in

Full text of DOI:10.1080/10610278.2014.909043

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Fabrication and morphology control of the
electrostatic self-assembled system containing
porphyrin electrolytes and sulfonated fullerene
derivatives
Ning Wanga, Xiaona Zhangb, Wei Zhengb, Dan Ouyangac & Renqiang Yanga
a CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess
Technology, Chinese Academy of Sciences, Qingdao 266101, P.R. China
b College of Materials Science and Engineering, Harbin University of Science and Technology,
Harbin 150080, P.R. China
c University of Chinese Academy of Sciences, Beijing 100049, P.R. China
Published online: 23 Apr 2014.
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To cite this article: Ning Wang, Xiaona Zhang, Wei Zheng, Dan Ouyang & Renqiang Yang (2015) Fabrication and morphology
control of the electrostatic self-assembled system containing porphyrin electrolytes and sulfonated fullerene derivatives,
Supramolecular Chemistry, 27:1-2, 72-79, DOI: 10.1080/10610278.2014.909043
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Supramolecular Chemistry, 2015
Vol. 27, Nos. 1–2, 72–79, http://dx.doi.org/10.1080/10610278.2014.909043
Fabrication and morphology control of the electrostatic self-assembled system containing
porphyrin electrolytes and sulfonated fullerene derivatives
Ning Wanga*, Xiaona Zhangb, Wei Zhengb, Dan Ouyanga,c and Renqiang Yanga*
aCAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences,
Qingdao 266101, P.R. China; College of Materials Science and Engineering, Harbin University of Science and Technology, Harbin
b
c
150080, P.R. China; University of Chinese Academy of Sciences, Beijing 100049, P.R. China
(Received 8 January 2014; accepted 23 March 2014)
A series of water-soluble porphyrin electrolytes with quaternary ammonium ions side chains (TEMZnPN and THMZnPN)
and sulfonated fullerene derivatives were synthesised and characterised. The self-assembled system was fabricated through
the electrostatic interaction between the quaternary ammonium ions on the porphyrin derivatives and the sulfonic ions on the
fullerene derivatives. The optical properties of the self-assembled system in aqueous solution were recorded by ultraviolet–
visible and fluorescence spectroscopy. Scanning electron microscopy indicated that the morphology of the self-assembled
films was highly relative to the distance between the quaternary ammonium ions and the porphyrin core, which could be
easily adjusted by changing the length of the alkyl chain in the porphyrin derivatives.
Keywords: porphyrin; fullerene; electrostatic; self-assembled; electrolyte
Introduction
to external stimuli such as the change of the PH value in
the solution environment (40) or the wavelength of the
excitation light (41). Ouyang’s group reported the
fabrication and enhanced nonlinear optical properties of
electrostatic self-assembled film containing water-soluble
chiral poly(phenylenevinylene)s and oligo-thiophene
derivatives (42).
Self-assembly of organic molecules is one of the most
efficient approaches to obtain supramolecular nanostruc-
tures with controlled dimensions and specific functions
(1–5). The as-prepared supramolecular materials can be
used in many fields, such as optoelectronic devices (6, 7),
drug delivery systems (8), hydrogels (9, 10) and sensors
(11–14). The assembly strategies of the supramolecular
systems rely on the presence of many different types of
weak interactions, including magnetic force (15–17),
host–guest coordination (18), van der Waals force (19–
22), hydrogen bonding (23–27), electrostatic (28–32) and
hydrophilic–hydrophobic interactions (33, 34). Among
these various interactions, electrostatic force is one of the
most versatile interactions to mediate the structure of self-
assembled systems (35). The electrostatic self-assembled
system could be fabricated through not only alternating
deposition of oppositely charged rigid planar molecules on
the surface of the substrates (36), but also mixing the
molecules with opposite charges in solution (37).
Furthermore, the morphology and the physical properties
of the electrostatic self-assembled systems could be tuned
by means of modifying the chemical structures of the
charged components or changing the external environment
of the system (38). For example, Grohn’s group reported a
variety of electrostatic assemble systems with different
shapes ranging from spheres to rods, networks and vesicles
(39), and the formation of nano assemblies could respond
The supramolecular system containing porphyrins and
fullerenes, owing to their characteristic structural features,
have always attracted great interest in the formation of
self-assembled complex (43–47). However, the studies on
the electrostatic self-assembled system containing por-
phyrin and fullerene derivatives are relatively rare (48).
Herein, we investigated an electrostatic self-assembled
system utilising porphyrin electrolytes with quaternary
ammonium salts side chains and fullerene sulfonic sodium
salts. As shown in Figure 1, the porphyrin and fullerene
derivatives could form the electrostatic complex through
the interaction of the side chains with opposite charges.
Specifically, the distance between the quaternary
ammonium groups and the porphyrin core could be
tuned by changing the length of the alkyl-connecting
chain. So that the optical properties and the expected
morphology of the electrostatic self-assembled system
would be adjusted. This could be approved by the different
titration curves of absorption and fluorescence spectra and
the scanning electron microscopy (SEM) images of the
supramolecular systems.
*Corresponding authors. Email: wangning@qibebt.ac.cn; yangrq@qibebt.ac.cn
q 2014 Taylor & Francis

Supramolecular Chemistry
73
Figure 1. (Colour online) Formation of the electrostatic self-assembled system based on the porphyrin electrolytes and fullerene
sulfonic sodium salts.
Results and discussion
diethyl etherate in chloroform, respectively (18). The
porphyrin electrolytes with quaternary ammonium salts
side chains THMZnPN and TEMZnPN were prepared
based on the typical reaction between the alkyl bromides
and amine (50). The quaternisation reaction was
completed which was proved by the 1H NMR of the
products (Figures S1 and S2). The fullerene Sulfonic
Sodium Salts C60SO3Na (Scheme 2) were synthesised
referring to the reported procedure (51). The products were
Synthesis
As shown in Scheme 1, vanillin was reacted with three
times equivalent of 1,2-dibromoehtane and 1,6-dibromo-
hexane catalysed by potassium carbonate and 18-crown-6
to afford compounds 1a and 1b, respectively (49). The
porphyrin derivatives 2a and 2b were conveniently
synthesised through condensation of 1a and 1b with
pyrrole at the aid of catalysed amount of borontrifluoride
1
characterised by H NMR, 13C NMR and high-resolution
Scheme 1. Synthesis route of porphyrin derivatives.

74
N. Wang et al.
added. The above results indicated the existence of
interaction between the porphyrin electrolytes and the
fullerene sulfonic sodium salts in the ground state (52).
As shown in Figure 3(a), the fluorescence spectrum of
pure compound TEMZnPN in aqueous solution showed
maximum peak at 614 nm with a shoulder peak at around
660 nm. On addition of C60SO3Na, the fluorescence
intensity of the TEMZnPN decreased, which confirmed
the formation of electrostatic self-assembled complex
(18). The similar fluorescence quench was found in the
case of THMZnPN (Figure 3(b)). Interestingly, the quench
of TEMZnPN was much more efficient than that of
THMZnPN with adding the same amount of C60SO3Na in
the solution, which was well consistent with the changing
trend of the absorption spectra.
Scheme 2. The chemical structure of fullerene derivatives.
mass spectra (HRMS). Both the porphyrin and the
fullerene electrolytes had good solubility in aqueous
solution.
The Stern–Volmer plots constructed from the
fluorescence quenching data are shown in Figure 3(c).
For both the porphyrin electrolytes with different lengths
of side chains, the Stern–Volmer plots were linear at low
quencher concentrations (,0.8 mM), which suggested that
the excited-state porphyrin was deactivated upon a
diffusive encounter with fullerene (53). It should be
noted that the static quenching constant (Ksv) for
TEMZnPN was 6.32 £ 105 M–1, which was 3.7 times
larger than Ksv for THMZnPN (Figure 3(c), inset). The
result meant that the TEMZnPN/C60SO3Na complex had
higher stability than that of THMZnPN/C60SO3Na (54).
Considering the only difference between the two
electrostatic systems that was the distance between the
porphyrin core and the quaternary ammonium function
groups, we could conclude that the length of the alkyl-
connecting chain played a key role in affecting the Ksv of
our self-assembled system. The length of TEMZnPN side
chain was shorter than that of THMZnPN, thus TEMZnPN
was more exposed to fullerene, while with a longer side
chain the steric effect would prevent fullerene from
approaching THMZnPN.
Optical properties
Figure 2 shows the absorption spectra change of porphyrin
derivatives in aqueous solution upon adding different
ratios of C60SO3Na at room temperature. As shown in
Figure 2(a), the absorption spectrum of TEMZnPN
without C60SO3Na had one strong Soret band at 426 nm
and two Q-band peaks at 560 and 601 nm. The maximum
for the Soret band shifted to longer wavelength and the
absorbance reduced with the addition of C60SO3Na.
Meanwhile, a shoulder peak at 443 nm appeared and the
absorbance enhanced with the increasing concentration of
the C60SO3Na in the solution. Consequently, a tight
isobestic point at 434 nm was displayed. A similar
changing trend of absorption spectra was found in the
case of THMZnPN, except that a relatively smaller change
amplitude was found compared with that of TEMZnPN
while adding the same amount of C60SO3Na (Figure 2
(b)). The plots of the absorption change at 426 nm versus
C60SO3Na concentration indicating the existence of the
limiting values for both TEMZnPN and THMZnPN (see
Figure S3). In the case of TEMZnPN, the curve was
convergent at 0.21 when 1.2 equiv. of C60SO3Na
was added; in the case of THMZnPN, the curve was
convergent at 0.33 when 2.4 equiv. of C60SO3Na was
As the concentration of the C60SO3Na increased, the
Stern–Volmer plots (Figure 3(c)) for both TEMZnPN and
Figure 2. (Colour online) (a) Changes in the UV–vis absorption spectra of TEMZnPN upon adding different ratio of C60SO3Na in
aqueous solution (0.2–1.8 equiv.). (b) Changes in the UV–vis absorption spectra of THMZnPN upon adding different ratio of C60SO3Na
in aqueous solution (0.2–3.0 equiv.). [TEMZnPN or THMZnPN] ¼ 2.0 £ 10–6 M. [C60SO3Na] ¼ 2.0 £ 10–4 M.

Supramolecular Chemistry
75
Figure 3. (Colour online) (a) Steady-state fluorescence spectra of TEMZnPN (2.0 £ 10–6 M) with the increasing addition of C60SO3Na
(2.0 £ 10–7–3.6 £ 10–6 M). (b) Steady-state fluorescence spectra of THMZnPN (2.0 £ 10–6 M) with the increasing addition of
C60SO3Na (2.0 £ 10–7–6.0 £ 10–6 M). (c) Stern–Volmer plots for the fluorescence quenching of TEMZnPN (square) at 614 nm and
THMZnPN (circle) at 618 nm by C60SO3Na (curves are fitted using the modified Stern–Volmer equation, PL represents the fluorescence
intensity at a given quencher concentration; PL0 represents the initial fluorescence intensity in the absence of quencher); inset: low
quencher concentration region and linear static Stern–Volmer fittings.
THMZnPN become superlinear. The upward deviation of
the plots indicated that the quenching was more effective
with a dramatically increased Ksv value, which reflected a
contribution of static quenching to the dynamic quenching
of the porphyrin by fullerene according to the previous
similar reported study on the electrostatic self-assembled
systems (55–57). As the concentration of fullerene
increased, a network of stronger electrostatic complex
was formed, leading to an additional increase in the
quenching constant (KSV), which was the reason for the
deviation from the Stern–Volmer relationship. It should
also be noted that the quenching constant (KSV) for
TEMZnPN was still larger than that for THMZnPN, which
should be also attributed to that a shorter side chain could
assist the rapid exciton diffusion from porphyrin core to
fullerene more effectively, thus facilitating the static
quenching.
lack of fullerene moiety and the decreased number of
sulfonic acid sodium salt in the reference compound.
The morphologies of self-assembled films
Figure 4(a) and (b) presented the morphology of the film
prepared through dropping the aqueous solution containing
TEMZnPN and C60SO3Na on the silicon wafer substrate.
A flower-like morphology was obtained with diameters in
the range of 50–200 nm. Interestingly, under the same
experimental conditions, the film containing THMZnPN
and C60SO3Na showed a fibre-like morphology with
diameters in the range of 50–100 nm (Figure 4(c) and (d)).
These results indicated that the morphology of the
electrostatic self-assembled system could be tuned by
altering the length of the alkyl-connecting chain in the
porphyrin electrolyte. The morphology change could be
ascribed to the binding constant difference between the
porphyrin electrolytes with different side chains and
fullerene sulfonic sodium salts.
The control experiments with 1,6-naphthalenedisulfo-
nic acid disodium salt as the reference compound. The
titration curves of absorption (Figure S4) and fluorescence
spectra (Figure S5) proved the formation of electrostatic
self-assembled systems while adding the aqueous solution
of 1,6-naphthalenedisulfonic acid disodium salt; however,
the change amplitude of the spectra was much lower than
that with C60SO3Na as quencher, which was due to the
Conclusion
A series of porphyrin derivatives with quaternary
ammonium salts groups have been synthesised and

76
N. Wang et al.
Figure 4. SEM images of the self-assembled film containing the fullerene derivatives C60SO3Na and the porphyrin derivatives
TEMZnPN in large scale (a) and small scale (b). FE-SEM images of the self-assembled film containing the fullerene derivatives
C60SO3Na and the porphyrin derivatives THMZnPN in large scale (c) and small scale (d).
characterised. The electrostatic self-assembled system
containing the porphyrin electrolytes and the fullerene
sulfonic sodium salts was fabricated. The absorption
spectra results indicated the existence of interaction
between the two chromophores in the ground state.
On addition of C60SO3Na to the aqueous solution
containing porphyrin derivatives, the fluorescence
intensity of both TEMZnPN and THMZnPN decreased.
The different quenching rate of the two porphyrin
electrolytes indicated that the length of the alkyl-
connecting chain between the porphyrin chromophore
core and the quaternary ammonium functional groups
played a key role in affecting the binding constant of self-
assembled system. The SEM results indicated that the
morphology of the electrostatic self-assembled system
could also be tuned by altering alkyl-connecting chain in
the porphyrin electrolyte. Our work provided a strategy to
tune the optical property and morphology of the
electrostatic self-assembled system.
Measurements
1H NMR and 13C NMR spectra were recorded on a Bruker
DRX-600 spectrometer (Bruker, Bremen, Germany). ESI
mass spectrometric measurements were carried out on AB
SCIEX 4000 QTRAP in positive ion mode (Agilent, Santa
Clara, CA, USA). Ultraviolet–visible (UV–vis) spectra
were measured on a Varian Cary 50 spectrophotometer
(Varian, Palo Alto, CA, USA). Fluorescence spectra were
recorded on a HJY-FluoroMax-4-NIR spectrofluorometer
(Horiba, Bensheim, Germany). The emission spectra (500–
800 nm) were taken with excitation at 426 nm. The optical
titration experiment was carried out as follows: TEMZnPN
or THMZnPN was dissolved in distilledwater toprepare the
aqueous solution of porphyrin derivatives, in which the
concentration of the solution was 2.0 £ 10–6 M. For each
addition in the absorption spectra measurement, 5 mL of
aqueous solution of C60SO3Na (2.0 £ 10–4 M) was added
into 2.5 mL of aqueous solution of TEMZnPN or
THMZnPN (the adding ratio is 0.2 equiv. of C60SO3Na to
1 equiv. of TEMZnPN or THMZnPN for each addition,
respectively). The similar procedure was followed in the
fluorescence spectra measurement except that 2.5 mL of
aqueous solution of C60SO3Na (2.0 £ 10–4 M) was added
to the anterior four times additions to investigate the
quenching of fluorescence at low concentration of
C60SO3Na. Field emission scanning electron microscopy
(FE-SEM) images were taken on a JSM 6700F NT
instrument (Hitachi, Tokyo, Japan). The sample was
prepared as follows: 0.1 mL of the aqueous solution
containing porphyrin electrolyte and C60SO3Na was
Experimental
Materials
All reagents were bought from commercial sources and
were used without further purification. The solvents were
purified with standard methods. Silica gel (200–300 mesh)
was used for column chromatography. The products were
1
characterised by H NMR, 13C NMR and electrospray
ionisation (ESI) HRMS.

Supramolecular Chemistry
77
dropped on the surface of silicon wafer substrate
Synthesis of 5,10,15,20-tetra(4-(2-bromoethoxy)-3-
methoxyphenyl)porphyrin (2b)
([porphyrin electrolyte, C60SO3Na] ¼ 2.0 £ 10– 6 M).
The sample was dried in oven at room temperature for
48 h before measurement.
Compound 1b (2.60 g, 10 mmol), pyrrole (670 mg,
10 mmol), borontrifluoride diethyl etherate (64 mL) and
chloranil (487 mg, 2 mmol) were reacted in CHCl3
(260 mL) following the experimental conditions identical
to that for the synthesis of 2a to obtain 2b as purple solid
(436 mg, 14.3%). 1H NMR (600 MHz, CDCl3):d 8.91
(s, 8H), 7.82 (s, 4H), 7.77 (d, J ¼ 7.90 Hz, 4H), 7.31
(d, J ¼ 7.90 Hz, 4H), 4.67 (t, J ¼ 6.60 Hz, 8H), 4.00
(s, 12H), 3.92 (t, J ¼ 6.60 Hz, 8H), 22.75 (s, 2H).
13C NMR (CDCl3):d 155.4, 150.8, 147.2, 144.5, 131.9,
125.7, 122.0, 117.7, 115.6, 113.5, 102.5, 61.5, 56.7, 27.2.
Synthesis of 4-(6-bromohexyloxy)-3-
methoxybenzaldehyde (1a)
Vanillin (15.2 g, 0.1 mol), 1,6-dibromohexane (72.3 g,
0.3 mol), potassium carbonate (13.8 g, 0.1 mol) and
18-crown-6 (2.64 g, 10 mmol) were added in 500 mL of
toluene and refluxed for 48 h. The reactant mixture was
allowed to cool to the room temperature and filtered.
The filtrate was evaporated to remove the 1,6-
dibromohexane and toluene. The residue was purified
by a silica column (chloroform as eluent) to afford 1a as
white solid (23.7 g, 75.5%). 1H NMR (600 MHz, CDCl3,
TMS): d 9.86 (s, 1H), 7.46 (dd, J1 ¼ 8.17 Hz,
J2 ¼ 1.75 Hz, 1H), 7.43 (d, J ¼ 1.75 Hz, 1H), 6.98 (d,
J ¼ 8.17 Hz, 1H), 4.13 (t, J ¼ 6.60 Hz, 2H), 3.95 (s, 3H),
3.44 (t, J ¼ 6.60 Hz, 2H), 1.95–1.89 (m, 4H), 1.58–1.51
(m, 4H).
Synthesis of zinc complex of 5,10,15,20-tetra(4-(6-
bromohexyloxy)-3-methoxyphenyl)porphyrin (3a)
Saturated zinc acetate dihydrate solution in methanol
(10 mL) was added to a solution of compound 2a (400 mg,
0.28 mmol) in chloroform (60 mL). The mixture was
stirred at room temperature for 3 h and then was washed
with water and dried over anhydrous Na2SO4. The solvent
was removed to afford 3a as purple powder. (407 mg,
96%). 1H NMR (600 MHz, CDCl3):d 9.02 (s, 8H), 7.80 (s,
4H), 7.75 (d, J ¼ 7.90 Hz, 4H), 7.25 (d, J ¼ 7.90 Hz, 4H),
4.35 (t, J ¼ 6.60 Hz, 8H), 3.98 (s, 12H), 3.53
(t, J ¼ 6.60 Hz, 8H), 2.13–2.00 (m, 16H), 1.73–1.55 (m,
16H). 13C NMR (CDCl3):d 155.1, 150.4, 146.1, 142.0,
132.5, 125.8, 120.9, 117.5, 112.9, 113.6, 102.5, 61.4, 56.4,
33.2, 32.7, 30.3, 27.2, 24.5.
Synthesis of 4-(2-bromoethoxy)-3-methoxybenzaldehyde
(1b)
Vanillin (15.2 g, 0.1 mol), 1,2-dibromoethane (55.8 g,
0.3 mol), potassium carbonate (13.8 g, 0.1 mol) and 18-
crown-6 (2.64 g, 10 mmol) were combined under exper-
imental conditions identical to that for the synthesis of 1a
to get 1b as white solid (21.0 g, 81%). 1H NMR (600 MHz,
CDCl3, TMS): d 9.89 (s, 1H), 7.48–7.45 (m, 2H), 7.01 (d,
J ¼ 7.90 Hz, 1H), 4.44 (t, J ¼ 6.60 Hz, 2H), 3.96 (s, 3H),
3.72 (t, J ¼ 6.60 Hz, 2H).
Synthesis of zinc complex of 5,10,15,20-tetra(4-(2-
bromoethoxy)-3-methoxyphenyl) porphyrin (3b)
Compound 2b (400 mg, 0.33 mmol), zinc acetate dihydrate
solution in methanol (10 mL) and CHCl3 (60 mL) were
combined under the experimental conditions identical to
that for the synthesis of 3a to obtain 3b as purple powder
Synthesis of 5,10,15,20-tetra(4-(6-bromohexyloxy)-3-
methoxyphenyl)porphyrin (2a)
1
(413 mg, 97%). H NMR (600 MHz, CDCl3):d 9.02 (s,
A solution of compound 1a (3.14 g, 10 mmol) and pyrrole
(670 mg, 10 mmol) in dry CHCl3 (260 mL) was purged
with nitrogen for 30 min, and then 64 mL of borontri-
fluoride diethyl etherate was added. The solution was
stirred for 2 h at room temperature, and chloranil (487 mg,
2 mmol) was added. The mixture was stirred overnight,
and then the solvent was removed. Column chromatog-
raphy on silica gel with chloroform as the eluent afforded
the pure product as purple solid (457 mg, 12.6%). 1H NMR
(600 MHz, CDCl3):d 8.92 (s, 8H), 7.80 (s, 4H), 7.75 (d,
J ¼ 7.90 Hz, 4H), 7.25 (d, J ¼ 7.90 Hz, 4H), 4.35 (t,
J ¼ 6.60 Hz, 8H), 3.99 (s, 12H), 3.53 (t, J ¼ 6.60 Hz, 8H),
2.13–1.99 (m, 16H), 1.75–1.65 (m, 16H), 22.72 (s, 2H).
113C NMR (CDCl3):d 155.3, 150.6, 147.1, 144.3, 131.8,
125.7, 122.1, 117.5, 115.2, 113.6, 102.5, 61.4, 56.5, 33.1,
32.0, 30.4, 27.3, 24.5.
8H), 7.82 (s, 4H), 7.77 (d, J ¼ 7.90 Hz, 4H), 7.31 (d,
J ¼ 7.90 Hz, 4H), 4.68 (t, J ¼ 6.60 Hz, 8H), 3.99 (s, 12H),
3.92 (t, J ¼ 6.60 Hz, 8H). 13C NMR (CDCl3):d 155.1,
150.6, 146.1, 142.1, 132.8, 125.9, 120.8, 117.5, 112.3,
111.1, 101.3, 61.5, 56.5, 27.1.
Synthesis of porphyrin derivatives with quaternary
ammonium salts THMZnPN
Compound 3a (60.4 mg, 0.04 mmol) was dissolved in
15 mL of THF and then the mixture was cooled to 0oC. The
water solution trimethylamine (50%, 6 mL) was added to
the above mixture with vigorous stirring. The reaction
mixture was allowed to stir at room temperature for 24 h.
The solvent was removed and the residue was washed with

78
N. Wang et al.
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dichloromethane for several times to get product
THMZnPN as purple solid (70.1 mg, 98%). 1H NMR
(600 MHz, CD3OD): 8.90 (s, 8H), 7.83 (s, 4H), 7.74 (d,
J ¼ 7.55 Hz, 4H), 7.35 (d, J ¼ 7.55 Hz, 4H), 4.34 (t,
J ¼ 6.06 Hz, 8H), 3.97 (s, 12H), 3.44 (t, J ¼ 6.06 Hz, 8H),
3.20 (s, 36H), 2.37–2.16 (m, 16H), 1.95–1.68 (m, 16H).
13C NMR (CD3OD): 158.2, 154.3, 149.1, 144.0, 137.7,
125.8, 121.2, 117.5, 119.4, 114.7, 102.6, 64.3, 61.4, 56.4,
55.4, 34.2, 32.7, 30.2, 27.5. HRMS (ESI): calcd for
C84H116N8O8Zn4þ, m/z ¼ [M 2 4Br]4þ/4 ¼ 357.2603,
found 357.2625.
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Compound 3b (51.6 mg, 0.04 mmol), THF (15 mL) and
6 mL of 50% trimethylamine solution in water were
combined under the experimental conditions identical to
that for the synthesis of THMZnPN to obtain TEMZnPN
1
as purple powder (61.3 mg, 98%). H NMR (600 MHz,
CD3OD): 8.90 (s, 8H), 7.89 (s, 4H), 7.79 (d, J ¼ 7.90 Hz,
4H), 7.49 (d, J ¼ 7.90 Hz, 4H), 4.79 (t, J ¼ 6.09 Hz, 8H),
3.98 (s, 12H), 3.96 (t, J ¼ 6.09 Hz, 8H). 3.47 (s, 36H). 13
C
NMR (CD3OD): 159.1, 154.3, 149.2, 145.4, 137.5, 124.4,
121.2, 119.6, 113.1, 112.6, 101.6, 67.2, 64.2, 57.5, 55.1.
HRMS (ESI): calcd for C68H84N8O8Zn4þ, m/z ¼ [M–
4Br]4þ/4 ¼ 301.1398, found 301.1436.
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Funding
This work was supported by the National Natural Science
Foundation of China [21204097, 51173199], the Chinese
Academy of Sciences (KGCX2-YW-399 þ 9-2), the Shandong
Provincial Natural Science Foundation [ZR2011BZ007] and the
Qingdao Municipal Science and Technology Program (11-2-4-
22-hz), and the Key Project Foundation of Heilongjiang Province
University Material Research and Application Key Laboratory
(2013).
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