Calix[4]arene Derivative Functionalized Lanthanide (Eu, Tb ... · 1534 1195 1077 1700 3288 1339 775 1211 1467 1594 3208 bance Wave number / cm -1 2870 2971 ... -NCH 2 Figure S11 (A)

1

Supporting Information

Calix[4]arene Derivative Functionalized Lanthanide (Eu, Tb) SBA-15

Mesoporous Hybrids with Covalent Bond: Assembly, Characterization,

and Photoluminescence

Yajuan Li, Bing Yan*, and Li Wang

Department of Chemistry, Tongji University, Siping Road 1239, Shanghai 200092, China

E-mail: [email protected]

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011

mailto:[email protected]

2

1H NMR data for precursors Calix-Si, Calix-NO2-Si, and Calix-NH2-Si:

1H NMR for Calix-Si (CDCl3, 400 MHz): δ 0.85-0.87 (2H, t, CH2), 1.27-1.58 (14H, m, -CH3, -CH2),

3.49-3.75 (6H, m, OCH2), 3.91(m, 2H, -NCH2), 3.92-4.41(8H, m, Ar-CH2-Ar), 6.73-7.07 (8H, s, Ar-H),

10.13 (3H, s, Ar-OH). 1H NMR for Calix-NO2-Si (CDCl3, 400 MHz): 0.67 (2H, t, -CH2), 0.92(2H, m,

-CH2), 1.28 (9H, t, -CH3), , 3.19 (2H, m, -NH2), 3.72-3.77(6H, m. –OCH2), 3.83-3.85 (8H, m, Ar-CH2-Ar),

7.41-6.97 (11H, m, Ar-H), 10.21 (3H, s, Ar-OH). 1H NMR for Calix-NH2-Si (CDCl3, 400 MHz): δ

0.78-0.85 (2H, t), 1.88-1.94 (2H, m), 1.88-1.95(9H, m, -CH3) 3.54 (2H, m, -NHCH2)，3.55-3.56(6H, m,

-OCH3), 3.57-3.59 (8H, m, Ar-CH2-Ar), 6.41-7.07 (11H, m, Ar-H), 10.18 (4H, s, Ar-OH).

(Figure S11 in the below)

The content of the lanthanide (Eu3+

, Tb3+

) in the hybrids:

The final hybrids samples are dissolved in nitric acid, then titrated with EDTA solution, using a buffer

(pH 5.8) and xylenol-orange as indicator. The contents of lanthanide ions (Eu3+

, Tb3+

) in the hybrids are

7determined by complexometric titrations. For Eu3+

, 9.74 % (Eu(Calix-S15)phen), 9.40 %

(Eu(Calix-NO2-S15)phen), 9.51 % (Eu(Calix-NH2-S15)phen). For Tb3+

, 9.63 % (Tb(Calix-S15)phen),

9.26 % (Tb(Calix-NO2-S15)phen), 9.35 % (Tb(Calix-NH2-S15)phen). In fact, the sol-gel reaction can not

be guaranteed to be completely [1] and so it is difficult to determine the exact composition of the

Calix-S15, Calix-NO2-S15 and Calix-NH2-S15 networks within the complicated hybrid system not like

small molecule complex.

[1] W. S. Kim, M. G. Kim, J. H. Ahn, B. S. Bae, C. B. Park, Langmuir 2007, 23, 4732-4736; M. C.

Goncalves, V. D. Bermudez, R. A. S. Ferreira, L. D. Carlos, D. Ostrovskii, J. Rocha, Chem. Mater.

2004, 16, 2530-2543.


3

OH

CH2

4

O=C=N(CH2)3Si(OC2H5)3

85oC N212hours

OH

CH2

3

CH2

O

C O

(OC2H5)3Si NH(CH2)3

Calix

Calix-Si

TEOS OH

CH2

3

CH2

O

CO

SiHN (CH2)3OOO

HO

HOCalix-S15

Ln(NO3)3

EtOH

OOHOHOH

CO

SiHN (CH2)3OOO

HO

HO

Ln

H2O

H2O

Ln(Calix-S15)phen

toluene

P123, HCl, H2O

N

N[NO3

-]3

3+

Scheme S1 Synthesis procedure and predicted structure of the ternary mesoporous hybird materials Ln(Calix-S15)phen.


4

OH

CH2

3

ClCH2CH2CH2Si(OCH3)3

25oC N212hours

Calix-NH2

NH2

OH

CH2

OH

CH2

3

NH(CH2)3Si(OCH3)3

OH

CH2

Calix-NH2-Si

TEOS

P123, HCl, H2O

OH

CH2

3

NH

OH

CH2

Calix-NH2-S15

Ln(NO3)3

OHOHOHOH

Ln

H2O

H2O

NH

Ln(Calix-NH2-S15)phen

CH2Cl2

Si

OOO

OH

OH

(CH2)3

Si

OOO

OH

OH

(CH2)3

EtOH

N

N

[NO3-]3

3+

Scheme S2 Synthesis procedure and predicted structure of the ternary mesoporous hybird materials

Ln(Calix-NH2-S15)phen.


5

4000 3500 3000 2500 2000 1500 1000 500

1375

Ab

so

rba

nce

Wavenumber / cm-1

Figure S1 The FTIR spectra of as-synthesized Calix-S15 material.

4000 3500 3000 2500 2000 1500 1000 500

C

B

A

464800

1092

16583425

15341195

10771700

3288

77513391211

1467

15943208

Absorb

ance

Wavenumber / cm-1

2870

29712924

Figure S2(a) The FTIR spectra of Calix (A), the precursor Calix-Si (B) and Calix-functionalized mesoporous hybrid

material Calix-S15 (C).


6

4000 3500 3000 2500 2000 1500 1000 500

C

B

1196

1085

160728422950

3420

1205

755

1609

14643167

1658 464

800

1092

Absorb

ance

Wavenumber / cm-1

A

Figure S2(b) The FTIR spectra of Calix-NH2 (A), the precursor Calix-NH2-Si (B) and Calix-NO2-functionalized

mesoporous hybrid material Calix-NH2-S15 (C).

5 10 15 200.0

0.2

0.4

0.6

0.8

Po

re V

olu

me /

(cm

3/g)

Pore Diameter / nm

A

B

C

Figure S3 Pore size distribution for calix[4]arene functionalized mesoporous materials Calix-S15 (A), Calix-NO2-S15

(B), and Calix-NH2-S15 (C).


7

0 5 10 15 20 25 30

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

Po

re V

olu

me /

(cm

3/g)

Pore Diameter / nm

A

B

C

D

E

F

Figure S4 Pore size distributionof ternary lanthanide mesoporous hybrids Eu(Calix-S15)phen (A), Tb(Calix-S15)phen

(B), Eu(Calix-NO2-S15)phen (C), Tb(Calix-NO2-S15)phen (D), Eu(Calix-NH2-S15)phen (E), and

Tb(Calix-NH2-S15)phen (F).

Figure S5 SEM image of ternary mesoporous hybrid Tb(Calix-S15)phen.


8

200 400 600 800 100070

75

80

85

90

95

100

TG

/ %

Temperature / oC

Figure S6 (a) Thermogravimetry trace (TG) of the ternary mesoporous hybrid Tb(Calix-NO2-S15)phen under

oxidizing atmosphere.

200 400 600 800 10000

20

40

60

80

100

We

igh

t /

%

Temperature / oC

Figure S6 (b) Thermogravimetry trace (TG) of the pure complex Tb(Calix-NO2)phen.


9

400 450 500 550 600 650

B

A

Rela

tive I

nte

nsity /

a.u

.

Wavelength / nm

Figure S7 Comparison of normalized luminescence spectra recorded after treatment of the samples at 400 °C in N2 for

2 hrs (A for Tb(Calix-NO2-S15)phen and B for Tb(Calix-NO2)phen).


10

350 400 450 500 550

Rela

tive I

nte

nsity /

a.u

.

Wavelength / nm

A 417 nm B 440 nma

350 400 450 500 550

B 432 nm A 415 nm

Rela

tive I

nte

nsity /

a.u

.

Wavelength / nm

b

350 400 450 500 550

Rela

tive I

nte

nsity /

a.u

.

Wavelength / nm

A 410 nm B 423 nmc

Figure S8 Phosphorescence spectra of (a): Calix (A) and the precursor Calix-Si (B); (b) Calix-NO2 (A) and the precursor

Calix-NO2-Si(B); (c) Calix-NH2 (A) and the precursor Calix-NH2-Si (B).


11

0.0 0.5 1.0 1.5 2.0

= 0.499ms

a

Lg

(In

tensity)

Time / ms

0 1 2 3 4

b

= 0.548ms

Lg

(In

tensity)

Time / ms


12

0 1 2 3 4

c

= 0.570ms

Lg(I

nte

nsity)

Time / ms

0.0 0.5 1.0 1.5 2.0

d

= 0.624ms

Lg

(In

tensity)

Time / ms

Figure S9 Luminescence decay curve of the Tb-contaning mesoporous hybrid materials: A for Tb(Calix-S15), B for

Tb(Calix-NH2-S15)phen, C for Tb(Calix-NO2-S15)phen, and D for Tb(Calix-S15)phen.


13

0.0 0.5 1.0 1.5 2.0

a

= 0.261ms

Lg(I

nte

nsity)

Time / ms

0.0 0.5 1.0 1.5 2.0

= 0.469ms

b

Lg

(In

ten

sity)

Time / ms


14

0.0 0.5 1.0 1.5 2.0

c

= 0.488ms

Lg(I

nte

nsity)

Time / ms

0.0 0.5 1.0 1.5 2.0

d

= 0.504ms

Lg(I

nte

nsity)

Time / ms

Figure S10 Luminescence decay curve of the Eu-containing mesoporous hybrid materials: A for Eu(Calix-S15), B for

Eu(Calix-NH2-S15)phen, C for Eu(Calix-NO2-S15)phen, and D for Eu(Calix-S15)phen.


15

Figure S11 1H NMR

12 10 8 6 4 2

ppm

-OH

-CH2

H-Ar

-CH3

ArCH2 -OCH

2

-NCH2

Figure S11 (A) 1H NMR of Calix-Si

10 8 6 4 2

11 10 9

ppm

ppm

H-benzyl

NH-Ar

-OCH2

-CH3

-NCH2

-CH2

-OH

Figure S11 (B) 1H NMR of Calix-NO2-Si


16

10 8 6 4 2 0

11.0 10.8 10.6 10.4 10.2 10.0 9.8 9.6 9.4 9.2 9.0

ppm

ppm

H-benzyl

-OCH2

-CH2-CH

3

H2O

-OH

-NH

Ar-CH2

Figure S11 (C) 1H NMR of Calix-NH2-Si


Documents

Calix[4]arene Derivative Functionalized Lanthanide (Eu, Tb ... · 1534 1195 1077 1700 3288 1339 775 1211 1467 1594 3208 bance Wave number / cm -1 2870 2971 ... -NCH 2 Figure S11 (A)