Electronic Supplementary Information

Syntheses, Structures and Properties of 5-Azotetrazolyl Salicylic Acid and Its Dilanthanide

Complexes

Wen-Bin Chen,a Zhi-Xin Li,a Xin-Wei Yu,a Meng Yang,a Yan-Xuan Qiu,a Wen Dong,*,a and Ya-Qiu

Sun*,b

aSchool of Chemistry and Chemical Engineering, Guangzhou Key Laboratory for Environmentally

Functional Materials and Technology, Guangzhou University, Guangzhou 510006, P. R. ChinabDepartment of Chemistry, Tianjin Normal University, Tianjin 300383, P. R. China

Electronic Supplementary Information – Table of Contents

1. Fig. S1. X-ray powder diffraction patterns for 3-7.

2. Fig. S2. 3D supramolecular structure of 1 and 2.

3. Fig. S3. The atomic labeling diagram of 4-7.

4. Fig. S4. 3D supramolecular structure of 3-7.

5. Fig. S5. Photoisomerization of 1.

6. Fig. S6. The thermochromism of aqueous solutions of 1.

7. Fig. S7. TD-DFT calculations for the absorption spectra of the alkaline aqueous solution of 1

8. Fig. S8. The photochromism of the crystal powder samples of 47.

9. Fig. S9. Luminescence for the solid samples of 5-7.

10. Fig. S10. The plot of χMT versus T for 4-7.

11. Fig. S11. M versus H plots for 3.

12. Fig. S12. Temperature-dependence of the in-phase () and out-of-phase () of ac

susceptibility of 3 at 250-1500 Hz.

13. Fig. S13. Natural logarithm of the ratio of over versus 1/T of the data for 3.

14. Fig. S14. M versus H plots for 4.

15. Fig. S15. M versus H/T plots for 4.

16. Fig. S16. The plot of 1/χM versus T for 5.

17. Fig. S17. M versus H plots for 5.

18. Table S1 Cartesian coordinates for tran-enol isomer of H3ASA.

19. Table S2 Cartesian coordinates for cis-enol isomer of H3ASA.

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2014

Powder X-ray diffraction

Powder X-ray diffraction (XRD) data were collected on a Rigaku/max-2550 diffractometer with Cu-Kα

radiation (λ = 1.5418 Å). The simulated and experimental P-XRD patterns of 3–7 are shown in Fig. S1.

Their peak positions are in good agreement with each other indicating the phase purity of the samples

used in the physical measurements.

TD-DFT calculations for the absorption spectra of the alkaline aqueous solution of 1

In order to gain a better understanding for the absorption spectra of the alkaline aqueous solution of 1

and the photoisomerization reaction, TD-DFT was employed to obtain insight into the electronic

structures of the trans-enol-E and cis-enol-E isomers of ASA3- anion. Fig. S7 shows state energy

diagrams for the trans-enol-E and the optimized cis-enol-E isomer of ASA3- anion. The calculated first

main electronic absorption for the trans-enol-Z of of ASA3- anion is HOMO-1 LUMO transition with

oscillator strength f = 0.5614 which originates from the salicylic π (80.28 to 38.53% contributors) to

azo n* (10.47 to 51.39% contributors) and tetrazolate π* (9.25 to 10.08% contributors) transition, and

the electronic transition energy of 2.8585 eV corresponds to a maximum absorption peak of around 434

nm (Fig. S7a). The second electronic transition with an oscillator strength of f = 0.0467 and the

electronic transition energy of 4.3320 eV corresponding to absorption peak of around 286nm is

attributed to the HOMO LUMO+2 transition that originates from salicylic π (97.41 to 78.35%

contributors) to azo n* (1.10 to 6.53% contributors) and tetrazolate π* (1.49 to 15.12% contributors)

transition (Fig. S7b). For cis-enol-E ASA3- former, the calculated first electronic absorption with

oscillator strength f = 0.0925 is attributed to the HOMO LUMO+1 transition that originates from

salicylic π (89.56 to 88.42% contributors) and azo n (8.43 to 1.22% contributors) to tetrazolate π* (2.01

to 10.36% contributors) transition, and the electronic transition energy of 3.5214 eV corresponds to a

maximum absorption peak of around 355 nm (Fig. S7c). The second electronic transition with an

oscillator strength of f = 0.3644 and the electronic transition energy of 4.9794 eV corresponding to

absorption peak of around 249 nm is attributed to the HOMO-10 LUMO transition that originates

from salicylic π (46.73 to 15.29% contributors) and tetrazolate π (42.52 to 23.36% contributors) to azo

n* (10.75 to 61.35% contributors) transitions (Fig. S7d). Based on the above DFT calculation, the

maximum absorption peak transfer from 445 to 355 nm under 365 nm UV light irradiation should

originate from trans-enol to cis–enol photoisomerization reaction of ASA3– anion (Scheme 1). However,

it is difficult to demonstrate the photochromism for the solid samples and E-Z transfer in solution using

TD-DFT calculation and the work should be paid to the further research.

10 20 30 40 50

(a)

2theta(deg)

Simulation Experimental

10 20 30 40 50

(b)

2theta(deg)

Simulation Experimental

10 20 30 40 50

(c)

2theta(deg)

Simulation Experimental

10 20 30 40 50

(d)

2theta(deg)

Simulation Experimental

10 20 30 40 50

(e)

2theta(deg)

Simulation Experimental

Fig. S1. (a)-(e) X-ray powder diffraction patterns for 3-7, respectively.

Fig. S2. (a) (b) 3D supramolecular structure of 1 and 2, respectively.

Fig. S3. (a), (b), (c) and (d) The atomic labeling diagram of 4-7, respectively. All H atoms and lattice

water molecules have been omitted for clarity.

Fig. S4. (a)-(e) 3D supramolecular structure of 3-7, respectively.

0 20 40 60 80 100

0.0

0.5

1.0

1.5

2.0

2.5

3.0---------------------------------------------------------A -0.12557 0.06977B 0.02824 0.00162---------------------------------------------------------

R SD N P---------------------------------------------------------0.98238 0.1402 13 <0.0001--------------------------------------------------------

ln(A

0-A8)/

(At-A

8)

T/min

Fig. S5. Photoisomerization of 1 ln((A0-A∞)/(At-A∞)) = A+Bt; B = 2.824×10-2

min-1

.

250 300 350 400 450 500 5500.0

0.2

0.4

0.6

0.8

Abso

rban

ce

Wavelength(nm)

℃ 32 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Fig. S6. The temperature-dependent changes of UV-vis absorption spectra of aqueous solutions of 1

with concentration of 5x10-5 mol·dm-3 and pH = 11.64 in the temperature range of 32-100 oC.

Fig. S7. (a), (b) State energy diagrams and contributing molecular orbitals for trans-enol-E of ASA3-;

(c), (d) State energy diagrams and contributing molecular orbitals for the optimized cis-enol-E isomer

of ASA3-.

Fig. S8. (a) The color and the corresponding to diffuse reflectance spectra for the powder samples of 4.

(b), (c) and (d) The color changes of the crystal powder samples of 57, respectively.

350 400 450 500 550 600

2000

4000

6000

8000

10000

12000

300 320 340 360 380 4000

1000

2000

3000

4000

Inte

nsity

Wavelength(nm)

Wavelength(nm)

Inte

nsity

(4) (5) (6)

Fig. S9. The emission spectra of 57 (inset is Excitation spectrum).

0 50 100 150 200 250 3000

5

10

15

20

25

30

(4) (5) (6) (7)

T/K

MT/

cm3 Km

ol-1

Fig. S10. The plot of χMT versus T for 4-7 in the magnetic field of 1000 Oe in 2300 K.

0 10000 20000 30000 4000002468

101214

H/Oe

M/ B 2.5K

3.0K 5.0K 8.0K

Fig. S11. M versus H plots in the field range 040 kOe for 3.

2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.53.0

3.5

4.0

4.5

5.0

5.5(a)

' /cm

3 mol

-1

T/K

250Hz 500Hz 1000Hz 1500Hz

2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.00.00.10.20.30.40.50.60.70.80.9 (b)

'' /cm

3 mol

-1

T/K

250Hz 500Hz 1000Hz 1500Hz

Fig. S12. (a) and (b) Temperature-dependence of the in-phase () and out-of-phase () of ac

susceptibility of 3 at 250-1500 Hz.

0.25 0.30 0.35 0.40 0.45 0.50-4.5

-4.0

-3.5

-3.0

-2.5

-2.0

-1.5

ln(

'' /' )

1/T (K-1)

113Hz 200Hz 518Hz 997Hz 1488Hz

Fig. S13. Natural logarithm of the ratio of over versus 1/T of the data for 3.

0 20000 40000 6000002468

101214

M/ B

H/Oe

2.5K 3.0K 5.0K 8.0K

Fig. S14. M versus H plots in the field range 070000 Oe for 4.

0 5000 10000 15000 20000 25000 30000

0

2

4

6

8

10

12

HT-1/Oe K-1

M/

B

2.5K 3.0K 5.0K 8.0K

Fig. S15. M versus H/T plots in the field range 070000 Oe for 4.

0 10000 20000 30000 40000 50000 60000 70000

0

2

4

6

8

M/

B

H/Oe

Fig. S16. M versus H plots in the field range 070000 Oe at 2K for 5.

0 50 100 150 200 250 300

0

5

10

15

20

25

1/ M

T/K

Fig. S17. The 1/χM versus T plot in the range from 300 to 2 K for 5.

Table S1 Cartesian coordinates for tran-enol isomer of H3ASA

N 4.87520000 3.87970000 3.52910000

N 6.01800000 4.02280000 4.05530000

N 6.82420000 4.89470000 1.91570000

N 8.28600000 4.11450000 3.36240000

N 8.06040000 5.02560000 1.42340000

N 8.93620000 4.54740000 2.27100000

C 2.65420000 3.13180000 3.87590000

H 2.60920000 3.02450000 2.95440000

C 3.82250000 3.61270000 4.44050000

C 2.81700000 3.49740000 6.59740000

H 2.86410000 3.62940000 7.51700000

C 1.63890000 2.99180000 6.03750000

C 1.54910000 2.80540000 4.64880000

C 3.90080000 3.80140000 5.81890000

H 4.68050000 4.12970000 6.20550000

C 7.00680000 4.31950000 3.11680000

C 0.30600000 2.25680000 4.02530000

O 0.60390000 2.69850000 6.83850000

O -0.68910000 2.09810000 4.78210000

O 0.30350000 2.00490000 2.80730000

Table S2 Cartesian coordinates for cis-enol isomer of H3ASA.

N 2.30923647 4.12831558 -2.27819836

N 3.05497933 3.13607471 -2.09689041

N 5.70353469 3.14551970 -1.83257315

N 4.32889781 1.49542957 -1.93535211

N 5.53434235 1.02522694 -1.66240523

N 6.39639737 2.01902294 -1.65309633

C 3.69108196 7.08446283 -5.67553230

C 3.40904939 7.73044711 -1.96851472

H 3.56810284 8.42261156 -1.36813252

C 2.96094107 6.51794684 -1.50354418

H 2.80688574 6.39203755 -0.59447697

C 3.40936237 6.88234648 -4.23475219

C 3.62757841 7.93041440 -3.32798780

C 2.95224203 5.66835896 -3.75377973

H 2.78860885 4.97362988 -4.34902298

C 4.40914609 2.78698705 -1.94199992

C 2.73652997 5.47386975 -2.40402650

O 4.02531619 8.17913422 -6.12252986

O 3.57610065 6.00885136 -6.39167706

O 4.03765817 9.15568844 -3.73122990