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Electronic Supplementary Information
Concentration and acid-base controllable fluorescence of
metallosupramolecular polymer
Lipeng He,a Jianjun Liang,a Yong Cong,a Xin Chen*b and Weifeng Bu*a
a Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province,State Key Laboratory of Applied Organic Chemistry, and College of Chemistry and Chemical
Engineering, Lanzhou University, Lanzhou City, Gansu Province, China, E-mail: [email protected] National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese
Academy of Sciences, Shanghai, 200083, China, E-mail: [email protected]
Instruments and Materials
All solvents and reagents were of reagent grade quality and purchased commercially. 1H NMR, 13C
NMR and DOSY spectra were recorded on a JNM-ECS400 spectrometer, performing in CDCl3,
CD3CN solutions and using TMS as an internal standard. Electrospray ionization mass spectra (ESI-
MS) were performed with Bruker microTOF-Q II. UV-vis absorption spectra were recorded by using
a SHIMADZU UV-2550 spectrophotometer. Luminescence measurements were made on a Hitachi F-
7000 spectrofluorimeter with a xenon lamp as the excitation source. Dynamic light scattering (DLS)
measurements were performed on a Brookhaven BI-200SM spectrometer. TEM images were obtained
with a JEOL JEM-1230 operating at 120 kV. All measurements were carried out at room temperature
except DOSY experiment.
All water-sensitive reactions were carried out under argon atmosphere. Zinc triflate (Zn(OTf)2 were
purchased from Aldrich and used without further purification.
Syntheses of ligand TPY-1 and metallosupramolecular polymer MP-Zn
Compounds 1 1 and 2 2 were synthesized and showed identical 1H NMR spectra to those reported
therein.
Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2014
I
O
O
I
OO
OO O
O
OO
OO
OOO
O
OO
O
OO
O
N
N
N
Pd(PPh3)4, CuI
Toluene, i-Pr2NH
1
2
O
O
OO
OO O
O
OO
OO
OOO
O
OO
O
OO
O
NN
N
N
N
N
TPY-1
HAr
HAr
HaHb
Hc
Hd
He
3
4 5
63'
5'6"
5"4"
3"ba
c
O
O
OO
OOO
O
OO
OO
OO O
O
OO
O
OO
O
N N
N
N
N
N O
O
OO
OOO
O
OO
OO
OO O
O
OO
O
OO
O
N N
N
N
N
N
ZnZn
n
2OTf-
MP-Zn
Zn(OTf)2
CHCl3 / MeCN
Scheme S1 Synthesis of ligand TPY-1 and polymer MP-Zn
L: To an argon degassed mixture of 4’-(4-ethynylphenyl)-[2,2’:6’,2’’]terpyridine (2, 0.5 mmol) and
compound 1 (0.25 mmol) in dry Toluene (20 mL) and dry diisopropylamine (10 mL) were added
tetrakis(triphenylphospine)palladium(0) (10 mol%) and copper(I) iodide (20 mol%) and the reaction
mixture was stired at 70 oC until TLC indicated complete conversion. After cooling to room
temperature, the precipitated ammonia salt was filtered off and washed intensively with CHCl3. The
solution was washed with sat. aq. NH4Cl/EDTA solution and dried over MgSO4. After removal of the
solvents, the product was precipitated from methanol. Further purification was achieved by column
chromatography (aluminum oxide, CH2Cl2/MeOH = 5:1 as eluent). 1H NMR (CDCl3, 400 MHz, δ):
3.78-3.80 (m, 16H, Hc), 3.82-3.88 (m, 16H, Hb), 4.08-4.14 (m, 16H, Ha), 4.79 (s, 4H, He), 5.19 (s, 4H,
Hd), 6.82-6.89 (m, 14H, HAr), 7.03 (s, 2H, c), 7.37 (m, 4H, 5, 5), 7.68-7.70 (d, 4H, a), 7.87-7.93 (m,
8H, 4, 4 b), 8.68 (d, 4H, 3, 3), 8.70 (d, 4H, 6, 6), 8.77 (s, 4H, 3, 5). 13C NMR (CDCl3, 100 MHz,
δ): 67.10, 67.29, 69.47, 69.51, 69.52, 69.59, 69.88, 69.94, 70.01, 71.37, 71.38, 71.41, 86.62, 95.84,
113.61, 114.12, 114.13, 114.50, 114.74, 118.11, 118.76, 121.49, 121.51, 122.12, 123.88, 124.07,
127.40, 127.51, 128.14, 132.45, 133.24, 137,05, 138.55, 148.98, 149.02, 149.04, 149.31, 149.44,
153.39, 156.16, 156.21, 168.58. HRESIMS: m/z calcd for [M + Na]+, 1832.6822; found 1832.6831.
UV-vis (CHCl3/CH3CN, 1:1): λmax/nm = 365 nm, 320 nm, 280 nm. Emission (CHCl3/CH3CN, 1:1)
(excitation in nm): λmax/nm = 435 nm. Anal. Calcd. for C106H100N6O22: C, 70.34; H, 5.57; N, 4.64.
Found: C, 70.16; H, 5.65; N 4.40.
Fig. S1 1H NMR Spectrum of TPY-1
Fig. S2 13C NMR Spectrum of TPY-1
MP-Zn: A solution of Zn(OTf)2 (9.10 mg, 25 mmol) in CD3CN (10 mL) was added Ligand TPY-1
(45.25 mg, 25 mmol) in CDCl3 (10 mL). The solution was stirred for 30 min at room temperature
prior to further analyzes. 1H NMR (CDCl3/CD3CN = 1:1, 400 MHz, δ): 3.69 (m, Hc), 3.79 (m, Hb),
4.07 (m, Ha), 4.8 (m, He), 5.23 (s, 4H, Hd), , 6.86 (m, HAr), 6.99 (m, c), 7.44 (m, 5, 5), 7.49 (m, a),
7.64 (m, 6, 6), 7.96 (m, b), 8.21 (m, 4, 4), 8.79 (m, 3, 3), 8.77 (m, 3, 5).
Fig. S3 1H NMR Spectrum of MP-Zn
Syntheses of Ghost C12-1
O
NH2
PF6-
C12-1
OO
OHO Br-C12H25
Acetone, reflux
1) MeOH, reflux2) NaBH43) HCl / H2O4) NH4PF6 / H2O
H2N
Scheme S2 Syntheses of Ghost C12-1
4-(dodecyloxy)benzaldehyde: To a mixture of 4-hydroxybenzaldehyde (10 mmol, 1.22 g) and
KCO3 (30 mmol, 4.14 g ) in acetone (80 mL) was added 1-bromododecane (15 mmol, 3.75 g) and the
reaction mixture was stired at reflux overnight. The mixture was cooled to room temperature, filtered
off and washed intensively with CHCl3. After removal of the solvents, the residue was purified by
column chromatography (petroleum ether/ethyl acetate, 7:1 v/v) to afford 4-(dodecyloxy)benzal-
dehyde as a white solid (2.32 g, 80%). 1H NMR (CDCl3, 400 MHz, δ): 9.87 (s, 1H), 7.82-7.84 (d, 2H),
6.98-7.00 (d, 2H), 3.97-4.01 (t, 2H), 1.72-1.95 (m, 2H), 1.28-1.44 (m, 18H), 0.88-0.91 (t, 3H).
C12-1: 4-(dodecyloxy)benzaldehyde (1.16 g, 4.0 mmol) and phenylmethanamine (430 mg, 4.0
mmol) were dissolved in methanol (50 mL) and heated at reflux under argon atmosphere overnight.
Then NaBH4 (380 mg, 10.0 mmol) was added to the solution in small portions and the mixture was
stirred at room temperature for another 12 h. Water (10 mL) was added to quench the remaining
NaBH4 and 2 M HCl was added to acidify the amine. The solvent was removed to give a white solid
which was dissolved in deionized water/methanol (90 mL, 5:1, v : v). A saturated aqueous solution of
NH4 PF6 was added to afford a white precipitate which was filtered off and washed with deionized
water to afford C12-1 as a white solid (1.70 g, 80%). 1H NMR (400 MHz, CD3CN, δ): 7.46 (s, 5H),
7.37-7.39 (d, 2H), 6.95-6.97 (d, 2H),4.21 (s, 2H), 4.17 (s, 2H), 3.97-4.01 (t, 2H), 1.72-1.95 (m, 2H),
1.28-1.44 (m, 18H),0.87-0.90 (t, 3H). 13C NMR (CD3CN, δ): 161.25, 132.87, 131.44, 131.15, 130,76,
130.08, 122.93, 115.80, 69.01, 52.19, 52.10, 32.65, 30.37, 30.35, 30.31, 30.29, 30.07, 30.06, 29.87,
26.68, 23.40, 14.40.
Fig. S4 1H NMR Spectrum of C12-1
Fig. S5 13C NMR Spectrum of C12-1
Syntheses of Ghost C12-2
O ONH2
H2N
C12-2
PF6-
PF6-
OO
OHO Br-C12H25-Br
Acetone, reflux
1) MeOH, reflux2) NaBH43) HCl / H2O4) NH4PF6 / H2O
H2N
OO
Scheme S3 Syntheses of Ghost C12-2
4,4'-(dodecane-1,12-diylbis(oxy))dibenzaldehyde: To a mixture of 4-hydroxybenzaldehyde (20
mmol, 2.44 g) and KCO3 (60 mmol, 8.28 g ) in acetone (160 mL) was added 1,12-dibromododecane
(10 mmol, 3.28 g) and the reaction mixture was stired at reflux for 24 h. The mixture was cooled to
room temperature, filtered off and washed intensively with CHCl3. After removal of the solvents, the
residue was purified by column chromatography (petroleum ether / ethyl acetate, 5:1 v / v) to afford
4,4'-(dodecane-1,12-diylbis(oxy))dibenzaldehyde as a white solid (2.05 g, 50%). 1H NMR (CDCl3,
400 MHz, δ):9.88 (s, 2H), 7.82-7.84 (d, 4H), 6.98-7.00 (d, 4H), 4.02-4.06 (t, 4H), 1.79-1.85 (m, 4H),
1.43-1.47 (m, 4H), 1.30 (m, 12H).
C12-2: 4,4'-(dodecane-1,12-diylbis(oxy))dibenzaldehyde (1.64 g, 4.0 mmol) and phenylmethan-
amine (860 mg, 8.0 mmol) were dissolved in methanol (50 mL) and heated at reflux under argon
atmosphere overnight. Then NaBH4 (760 mg, 20.0 mmol) was added to the solution in small portions
and the mixture was stirred at room temperature for another 12 h. Water (10 mL) was added to quench
the remaining NaBH4 and 2 M HCl was added to acidify the amine. The solvent was removed to give
a white solid which was dissolved in deionized water/methanol (90 mL, 5:1, v : v). A saturated
aqueous solution of NH4 PF6 was added to afford a white precipitate which was filtered off and
washed with deionized water to afford C12-2 as a white solid (2.12 g, 60%). 1H NMR (400 MHz,
CD3CN, δ): 7.46 (s, 4H), 7.36-7.38 (d, 4H), 6.95-6.97 (d, 4H), 4.20 (s, 4H), 4.16 (s, 4H),3.97-4.00 (t,
4H), 1.73-1.77 (m, 4H), 1.42-1.44 (s, 4H), 1.27 (s, 12H). 13C NMR (CD3CN, δ): 161.20, 132.83,
131.60, 131.11, 130.07, 123.10, 118.32, 69.01, 52.21, 52.10, 30.32, 30.10, 29.89, 26.70.
Fig. S6 1H NMR Spectrum of C12-2
Additional Experimental Data and Figures
Fig. S8 Partial DOSY NMR spectrum of TPY-1 (1.25 mM, CDCl3/CD3CN = 1:1, 293 K)
Fig. S9 Partial DOSY NMR spectrum of MP-Zn (1.25 mM, CDCl3/CD3CN = 1:1, 293 K).
0
10
20
30
40
MP-Zn
D / 1
0-10 m
2 s-1
TPY-1
Fig. S10 Diffusion coefficient D values of TPY-1 and MP-Zn (1.25 mM, CDCl3/CD3CN = 1:1, 293 K)
300 400 500 600 7000.0
0.3
0.6
0.9
1.2
Abso
rpta
nce
Wavelength / nm
Fig. S11 UV-vis absorption of ligand TPY-1 (12.5 μM, CHCl3/CH3CN = 1:1)
300 400 500 600 7000.0
0.3
0.6
0.9
1.2
Wavelength / nm
Abso
rpta
nce
Fig. S12 UV-vis absorption of MP-Zn. (monomer concentration, 12.5 μM, CHCl3/CH3CN = 1:1)
1 10 100 10000
25
50
75
100 TPY-1 1.25 mM MP-Zn 1.25 mM MP-Zn 125 M MP-Zn 12.5 M
Inte
nsity
%
Diameter / nm
Fig. S13 Size distributions of hydrodynamic diameter of TPY-1 and MP-Zn
Fig. S14 Partial 1H NMR spectra (400 MHz, CDCl3/CD3CN 1:1) of (a) guest C12-1, (b) 1.25 mM
MP-Zn (monomer concentration) with 2.0 equivalent C12-1 (DBA/DB24C8 1:1 molar ratio), (c)
obtained by addition 2.4 equivalent P1-tBu to (b), (d) obtained by addition 2.8 equivalent CF3COOH
to (c), (e) 1.25 mM MP-Zn. Here “u” and “c” denote uncomplexed and complexed moieties,
respectively
Fig. S15 (a) Fluorescence emission spectra of 1.25 μM MP-Zn (monomer concentration) in
CHCl3/CH3CN (1:1, v/v) upon titration with C12-1 (b) Fluorescence responsiveness of MP-Zn by
performing the acid-base reactions
Fig. S16 Fluorescence emission spectra of MP-Zn in CHCl3/CH3CN (1:1, v/v) upon titration with
C12-1 and C12-2
100 10000
25
50
75
100 MP-Zn MP-Zn + C12-1 MP-Zn + C12-2
Inte
nsity
%
Diameter / nmFig. S17 Size distributions of hydrodynamic diameter in CHCl3/CH3CN (1:1, v/v), the concentrations were 1.25 mM.
Fig. S18 TEM images of cross-linked MP-Zn (1.25 mM).
Additional discussions
1) Page 3 Column 2, “In our case, the host-guest recognition between DB24C8 and DBA groups may
result in the more rigidity and/or polarity and thus aggregation of the resulting complexes in the
solutions. ”
The threaded structure formed by the complexation between dibenzo-24-crown-8 (DB24C8) and
dibenzylammonium salt (DBA) could make the crown ether ring more rigidity. The incorporation of
DBA brought more polarity to the resulting complexes. This conclusion could be seen in the reported
crystal structure and 1H NMR data.3 In our case, the high-field shifts of the DB24C8 resonances also
supported this conclusion.
2) As addressed by Schubert and his coworkers, due to a considerably weaker binding strength of the
terpridine ligand to the Zn2+ ion, the degree of polymerization (DP) and molecular weight of the Zn-
based metallosuparmolecular polymer were not characterized by conventional techniques such as
mass spectrum and size exclusion chromatography (SEC).
3) Crystal measurement is a fairly good technique to characterize the compound. However, we cannot
obtain the crystal and its data. Generally, the compound must be pure enough so as to crystallise. In
our case, the resulting MP-Zn wasn’t only a mixture of different molecular weight, but also a
metallosupramolecular polymer. We did our best to crystallise these species. Unfortunately, we had a
failure.
References
1. X. Ji, Y. Yao, J. Li, X. Yan and F. Huang, J. Am. Chem. Soc., 2013, 135, 74.
2. F. Schlütter, A. Wild, A. Winter, M. D. Hager, A. Baumgaertel, C. Friebe and U. S. Schubert, Macromolecules, 2010, 43, 2759.
3. P. R. Ashton, P. J. Campbell, E. J. T. Chrystal, P. T. Glink, S. Menzer, D. Philp, N. Spencer, J. F. Stoddart, P. A. Tasker and D. J. Williams, Angew. Chem., Int. Ed. Engl., 1995, 34, 1865.