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: buwf@lzu.edu.cnb National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese

Academy of Sciences, Shanghai, 200083, China, E-mail: xinchen@mail.sitp.ac.cn

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

Fig. S7 13C 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.