Azobenzene-Derivated trisDiketonates Lanthanide Complexes：

Reversible transtocis Photoisomerization in Solution and Solid State

Li-Rong Lin,*,† Xuan Wang ,† Gao-Ning Wei ,† Hui-Hui Tang ,† Hui Zhang ,† Li-Hua Ma*,‡

† Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China

‡ Department of Chemistry, School of Science and Computer Engineer, University of Houston at Clear Lake, 2700 BAY AREA BLVD, Houston, TX, 77058

1. Crystal structures for Figures S1S2…………………………………..Page 1

2. UVVis absorption spectra for Figures S3S……………………….Page 2

3. UVVis absorption spectral change for Figures S6S22…………...Page 3-12

4. The trans-cis photoisomerization kinetics curves Figures S2333…Page13-15

5. 1H NMR spectra of compounds Figures S3443……………...…Page 16-19

6. IR spectra of compounds Figures S44 S53……………………..…Page 20-23

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2016

1

Figure S1. Crystal structure of Eu(LB)3(CH3CH2OH)(H2O). Selected bonds distances (Å) and angles (°) : Eu1O1B 2.315(4), Eu1O2A 2.333(5), Eu1 O2 2.360(4), Eu1 O1A 2.364(4) , Eu1O1 2.369(4), Eu1O2B 2.408(4), Eu1O1W 2.427(5), Eu1O2C 2.462(4); O1BEu1O2A 95.88(17), O1B Eu1O2 141.63(14), O1B Eu1O1A 73.67(16), O2AEu1O1A 69.47(14), O1BEu1O1W 142.86(18), O2AEu1O1W 82.10(18), O2Eu1O1W 74.99(16), O1BEu1O2C 91.02(17).

Figure S2. Crystal structure of Yb(LB)3 (CH3CH2OH)2. Selected bonds distances (Å) and angles (°) : Yb01O5 2.229(8), Yb01O4 2.271(8), Yb01O3 2.280(6),Yb01O2 2.279(8), Yb01O6 2.281(8), Yb01O1 2.304(8), Yb01O8 2.344(9), Yb01O7 2.252(10); O1Yb01O7 135.6(6), O2Yb01O8 145.7(3), O3Yb01O8 69.4(3), O4Yb01O2 108.3(3), O5Yb01O4 142.6(2), O6Yb01O1 136.6(2), O3Yb01O6 125.4(3) , O5Yb01O8 102.1(4).

2

250 300 350 400 450 500 550 600 6500.00.51.01.52.02.53.0

250 300 350 400 450 500 550 600 6500.00.51.01.52.02.53.0

LA La(LA)3 Eu(LA)3 Gd(LA)3 Yb(LA)3

Abs.

Ethanol

LB La(LB)3 Eu(LB)3 Gd(LB)3 Yb(LB)3

Wavelength / nm

Figure S3. UVVis absorption spectra of LA, LALn(III) and LB, LBLn(III) (5.0 × 105 mol L1) in ethanol solutions.

250 300 350 400 450 500 550 600 6500.00.51.01.52.02.53.0

250 300 350 400 450 500 550 600 6500.00.51.01.52.02.53.0

Abs.

LA La(LA)3 Eu(LA)3 Gd(LA)3 Yb(LA)3

Hexane

Wavelength / nm

LB La(LB)3 Eu(LB)3 Gd(LB)3 Yb(LB)3

Figure S4. UVVis absorption spectra of LA, LALn(III) and LB, LALn(III) (5.0 × 105 mol L1) in hexane solutions.

250 300 350 400 450 500 550

0.0

0.2

0.4

0.6

0.8

d

Abs

.

Wavelength / nm

0 s 2 s 5 s 10 s 30 s 1 min 2 min 5 min 10min 30min 60min

250 300 350 400 450 500 550

0.0

0.2

0.4

0.6

0.8

c

Abs.

Wavelength / nm

0 s 5 s 10 s 30 s 2min 10min 20min 60min

Figure S5. UVVis spectral change of LA in ethanol (2.0× 105 mol L1) solution upon irradiation at 365 nm (c) and recoverable irradiation at 450 nm (d) as a function of time.

3

250 300 350 400 450 500 550

0.0

0.2

0.4

0.6

0.8

1.0

1.2

eAb

s.

Wavelength / nm

0 s 5 s 10 s 1 min 5 min 10min 30min

250 300 350 400 450 500 550

0.0

0.2

0.4

0.6

0.8

1.0

1.2

f

Abs.

Wavelength / nm

0 s 2 s 5 s 10 s 1 min 5 min 30min

Figure S6. UVVis spectral change of LA in hexane (2.0× 105 mol L1) solution upon irradiation at 365 nm (e) and recoverable irradiation at 450 nm (f) as a function of time.

250 300 350 400 450 500 550 600 650 700

0.0

0.5

1.0

1.5

2.0

dAb

s.

Wavelength / nm

0 s 5 s 10 s 1min 2min 5min 10min 30min 90min 150min

250 300 350 400 450 500 550 600 650 700

0.0

0.5

1.0

1.5

2.0

c

Abs.

Wavelength / nm

0 s 10 s 20 s 1min 2min 5min 10min 30min 90min 150min

Figure S7. UVVis spectral change of LB in ethanol (2.0× 105mol L1) solution upon irradiation at 365 nm (c) and recoverable irradiation at 450 nm (d) as a function of time.

250 300 350 400 450 500 550 600 650

0.0

0.2

0.4

0.6

0.8

1.0

Abs.

Wavelength / nm

0 s 5 s 10 s 30 s 1min 2min 5min 10min 20min 30min 60min

e

250 300 350 400 450 500 550 600 6500.0

0.2

0.4

0.6

0.8

1.0

0 s 5 s 10 s 30 s 1min 2min 5min 10min 20min 30min

Abs.

Wavelength nm.

f

Figure S8. UVVis spectral change of LB in hexane (2.0× 105mol L1) solution upon irradiation at 365 nm (e) and recoverable irradiation at 450 nm (f) as a function of time.

4

250 300 350 400 450 500 550 600 650 7000.0

0.5

1.0

1.5

2.0

2.5

0 5 10 15 201.5

1.6

1.7

1.8

1.9

2.0

2.1

Abs.

Cycle number

Abs.

Wavelength / nm

no irradiation450 nm-2 min

365nm-10 min

Figure S9. Absorption spectra of Yb(LA)3 in acetonitrile solution under no irradiation, and in the photostationary states after alternating irradiation atandnm in repeating switching cycles (Inset: reversible change of absorption intensity at 358 nm).

250 300 350 400 450 500 550

0.0

0.5

1.0

1.5

2.0

2.5

d

Abs.

Wavelength / nm

0 s 2 s 5 s 10 s 30 s 1 min 2 min 5 min 10min 30min 60min

250 300 350 400 450 500 5500.0

0.5

1.0

1.5

2.0

2.5

c

Abs.

Wavelength / nm

0 s 5 s 10 s 30 s 1 min 2 min 5 min 10min 30min 60min

Figure S10. UVVis spectral change of Yb(LA)3 in ethanol (2.0× 105mol L1) solution upon irradiation at 365 nm (c) and recoverable irradiation at 450 nm (d) as a function of time.

250 300 350 400 450 500 550

0.0

0.4

0.8

1.2

1.6

2.0

2.4

f

Abs

.

Wavelength / nm

0 s 2 s 5 s 10 s 30 s 1 min 2 min 5 min 30min

250 300 350 400 450 500 5500.0

0.4

0.8

1.2

1.6

2.0

2.4

e

Abs

.

Wavelength / nm

0 s 5 s 10 s 30 s 1 min 2 min 5 min 10min 30min

Figure S11. UVVis spectral change of Yb(LA)3 in hexane (2.0× 105mol L1) solution upon irradiation at 365 nm (e) and recoverable irradiation at 450 nm (f) as a function of time.

5

250 300 350 400 450 500 5500.0

0.4

0.8

1.2

1.6

2.0

2.4

a

Abs.

Wavelength / nm

0 s 5 s 10 s 30 s 2 min 10min 30min 60min

250 300 350 400 450 500 550

0.0

0.4

0.8

1.2

1.6

2.0

2.4

b

Abs.

Wavelength / nm

0 s 2 s 5 s 10 s 30 s 2 min 10min 30min

250 300 350 400 450 500 550

0.0

0.4

0.8

1.2

1.6

2.0

d

Abs.

Wavelength / nm

0 s 2 s 5 s 10 s 2 min 10min 30min

250 300 350 400 450 500 5500.0

0.4

0.8

1.2

1.6

2.0

2.4

c

Abs.

Wavelength / nm

0 s 5 s 30 s 2 min 10 min 30min 60min

250 300 350 400 450 500 550

0.00.30.60.91.21.51.82.12.42.7

f

Abs.

Wavelength / nm

0 s 2 s 5 s 10 s 1 min 5 min 30min

250 300 350 400 450 500 550 6000.0

0.30.60.9

1.21.5

1.82.1

2.42.7

e

Abs.

Wavelength / nm

0 s 5 s 10 s 2 min 10min 20min 30min

Figure S12. UVVis spectral change of La(LA)3 in acetonitrile(a, b), ethanol (c, d) and hexane (e, f) (2.0× 105mol L1) solutions upon irradiation at 365 nm (a, c, e) and recoverable irradiation at 450 nm (b, d, f) as a function of time.

6

250 300 350 400 450 500 5500.0

0.5

1.0

1.5

2.0

2.5

a

Abs

.

Wavelength / nm

0 s 5 s 10 s 30 s 1 min 2 min 10min 30min 60min

250 300 350 400 450 500 550

0.0

0.5

1.0

1.5

2.0

2.5

b

Abs

.

Wavelength / nm

0 s 2 s 5 s 10 s 30 s 1 min 10min 30min 60min

250 300 350 400 450 500 5500.0

0.4

0.8

1.2

1.6

2.0

2.4

c

Abs

.

Wavelength / nm

0 s 5 s 10 s 30 s 1 min 2 min 5 min 10 min 30 min 60 min

250 300 350 400 450 500 5500.0

0.4

0.8

1.2

1.6

2.0

d

Abs

.Wavelength / nm

0 s 2 s 5 s 10 s 30 s 1 min 2 min 5 min 10min 30min

250 300 350 400 450 500 550

0.0

0.3

0.6

0.9

1.2

1.5

1.8

e

Abs

.

Wavelength / nm

0 s 5 s 10 s 30 s 1 min 5 min 10min 30min

250 300 350 400 450 500 550

0.0

0.3

0.6

0.9

1.2

1.5

1.8

f

Abs

.

Wavelength / nm

0 s 2 s 5 s 10 s 30 s 1 min 2 min 5 min 10min 30min

Figure S13. UVVis spectral change of Eu(LA)3 in acetonitrile(a, b), ethanol (c, d) and hexane (e, f) (2.0× 105mol L1) solutions upon irradiation at 365 nm (a, c, e) and recoverable irradiation at 450 nm (b, d, f) as a function of time.

7

250 300 350 400 450 500 5500.0

0.5

1.0

1.5

2.0

2.5

a

Abs

.

Wavelength / nm

0 s 5 s 10 s 1 min 2 min 5min 10min 30min 60min

250 300 350 400 450 500 550

0.0

0.5

1.0

1.5

2.0

b

Abs

.

Wavelength / nm

0 s 2 s 5 s 10 s 30 s 2min 10min 60min

250 300 350 400 450 500 5500.0

0.4

0.8

1.2

1.6

2.0

2.4

c

Abs

.

Wavelength / nm

0s 5s 10s 1min 2min 5min 10min 30min 60min

250 300 350 400 450 500 550

0.4

0.8

1.2

1.6

2.0

2.4

d

Abs

.

Wavelength / nm

0 s 2 s 5 s 10 s 30 s 1 min 5 min 30min 60min

250 300 350 400 450 500 5500.0

0.4

0.8

1.2

1.6

2.0

2.4

e

Abs

.

Wavelength / nm

0 s 5 s 10 s 1 min 2 min 10min 20min 30min

250 300 350 400 450 500 550

0.0

0.4

0.8

1.2

1.6

2.0

2.4

f

Abs

.

Wavelength / nm

0 s 2 s 5 s 10 s 1 min 10min 30min

Figure S14. UVVis spectral change of Gd(LA)3 in acetonitrile(a, b), ethanol (c, d) and hexane (e, f) (2.0× 105mol L1) solutions upon irradiation at 365 nm (a, c, e) and recoverable irradiation at 450 nm (b, d, f) as a function of time.

0.00.51.01.52.02.5

300 350 400 450 500 550 600 6500.00.51.01.52.02.5

Abs.

0 s 5 s 10 s 30 s 1 min 2 min 5 min 10 min 30 min 90 min

(a)

Wavelength / nm

0 s 5 s 10 s 30 s 1 min 2 min 5 min 10min 30min 60min

(b)

Figure S15. UVVis spectral change of Yb(LB)3 in acetonitrile (2.0×105 mol L1) upon irradiation at 365 nm (a) and recoverable irradiation at 450 nm (b) as a function of time.

8

300 350 400 450 500 550 600 6500.0

0.4

0.8

1.2

1.6

2.0

2.4

aAb

s.

Wavelength / nm

0 s 5 s 10 s 20 s 1min 2min 5min10min 30min 60min 120min

250 300 350 400 450 500 550 600 650 7000.0

0.4

0.8

1.2

1.6

2.0

2.4

b

Abs.

Wavelength / nm

0 s 5 s 10 s 20 s 1 min 2 min 5 min 10min 30min 60min

300 350 400 450 500 550 600 6500.0

0.4

0.8

1.2

1.6

2.0

2.4

c

Abs

.

Wavelength / nm

0 s 5 s 10 s 20 s 1 min 2 min 5 min 10 min 30 min 60 min 120 min 210 min

250 300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

2.5

d

Abs.

Wavelength / nm

0 s 5 s 10 s 20 s 1min 2min 5min 10min 30min 60min 90min

250 300 350 400 450 500 550 600 6500.0

0.4

0.8

1.2

1.6

2.0

2.4

f

Abs.

Wavelength / nm

0 s 5 s 10 s 30 s 1 min 2 min 5 min 30min

300 350 400 450 500 550 6000.0

0.4

0.8

1.2

1.6

2.0

2.4

e

Abs.

Wavelength / nm

0s 10min 30min 90min 180min

Figure S16. UVVis spectral change of La(LB)3 in acetonitrile (a, b), ethanol (c, d) and hexane (e, f) (2.0× 105mol L1) solutions upon irradiation at 365 nm (a, c, e) and recoverable irradiation at 450 nm (b, d, f) as a function of time.

9

250 300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

2.5

a

Abs

.

Wavelength / nm

0 s 5 s 10 s 20 s 1 min 2 min 5 min 10min 30min 60min 120min 240min

250 300 350 400 450 500 550 600 650 7000.0

0.5

1.0

1.5

2.0

2.5

b

Abs

.

Wavelength / nm

0 s 5 s 10 s 30 s 1 min 2 min 5 min 10min 30min 60min 120min 180min 200min

300 350 400 450 500 550 600 6500.0

0.4

0.8

1.2

1.6

2.0

c

Abs

.

Wavelength / nm

0 s 5 s 10 s 1 min 2 min 5 min 10 min 30 min 60 min 120 min 180 min

250 300 350 400 450 500 550 600 6500.0

0.4

0.8

1.2

1.6

2.0

d

Abs

.

Wavelength / nm

0 s 5 s 10 s 1 min 2 min 5 min 10min 30min 60min

300 350 400 450 500 550 600 6500.0

0.4

0.8

1.2

1.6

2.0

e

Abs

.

Wavelength / nm

0 s 5 s 10 s 1 min 2 min 5 min 10 min 30 min 60 min 120 min 180 min

250 300 350 400 450 500 550 600 6500.0

0.4

0.8

1.2

1.6

2.0

f

Abs

.

Wavelength / nm

0 s 5 s 10 s 1 min 2 min 5 min 10min 30min 60min

Figure S17. UVVis spectral change of Eu(LB)3 in acetonitrile (a, b), ethanol (c, d) and hexane (e, f) (2.0× 105mol L1) solutions upon irradiation at 365 nm (a, c, e) and recoverable irradiation at 450 nm (b, d, f) as a function of time.

10

300 350 400 450 500 550 6000.0

0.5

1.0

1.5

2.0

c

Abs

.

Wavelength / nm

0 s 5 s 10 s 1 min 2 min 5 min 10 min 30 min 60 min 120 min 180 min

250 300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

dA

bs.

Wavelength / nm

0 s 5 s 10 s 1 min 2 min 5 min 10min 30min 60min

Figure S18. UVVis spectral change of Gd(LB)3 in acetonitrile (a, b), ethanol (c, d) and hexane (e, f) (2.0× 105mol L1) solutions upon irradiation at 365 nm (a, c, e) and recoverable irradiation at 450 nm (b, d, f) as a function of time.

300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

2.5

Abs.

Wavelength / nm

0 s 5 s 10 s 1 min 5 min 10min 20min 30min 60min 120min 210min 240min

a

300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

0 s 5 s 10 s 30 s 1 min 2 min 5 min 10 min 30 min 60 min 120 min 180 min

Abs.

Wavelength / nm

b

300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

Abs.

Wavelength / nm

0 s 2 s 5 s 10 s 20 s 30 s 1 min 2 min 5 min 10min 30min 60min 120min 180min

e

300 350 400 450 500 550 600 650

0.0

0.3

0.6

0.9

1.2

1.5

Abs.

Wavelength / nm

0 s 2 s 5 s 10 s 20 s 1 min 2 min 5 min 10min 20min

f

11

300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

aA

bs.

Wavelength / nm

0s 5s 10s 20s 1min 2min 5min 10min 30min 60min 120min

300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

b

Abs

.

Wavelength / nm

5 s 10 s 30 s 1 min 2 min 5 min 10min 30min 60min 90min

300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

c

Abs

.

Wavelength / nm

0 s 5 s 30 s 1 min 2 min 5 min 10min 30min 60min

300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

d

Abs

.

Wavelength / nm

5 s 10 s 30 s 1min 5min 10min 30min 60min 150min 210min

Figure S19. UVVis spectral change of Yb(LB)3 in acetonitrile (a, b), ethanol (c, d) and hexane (e, f) (2.0× 105mol L1) solutions upon irradiation at 365 nm (a, c, e) and recoverable irradiation at 450 nm (b, d, f) as a function of time.

300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

e

Abs

.

Wavelength / nm

0s 5s 10s 30s1min 2min 5min 10min 30min 60min 120min 180min 210min

300 350 400 450 500 550 600 6500.0

0.5

1.0

1.5

2.0

f

Abs

.

Wavelength / nm

0 s 5 s 10 s 20 s 1min 2min 5min 10min 30min 60min

12

300 400 500 600 700 8000.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0 5 10 15 20

0.112

0.116

0.120

0.124

0.128

0.132

0.136

Cycle numbers

Abs

.

Abs.

Wavelength / nm

365nm-stable

450nm-stble

Figure S20. UVVis spectral change of La(LA)3 in PMMA film (5.0wt%) upon irradiation at 365 nm and recoverable irradiation at 450 nm (Inset: reversible change of absorption intensity at 358 nm in the photostationary states after alternating irradiation at andnm in repeated switching cycles).

250 300 350 400 450 500 550 600 6500.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0 5 10 15 200.110

0.115

0.120

0.125

0.130

0.135

0.140

0.145

Wavelength / nm

Abs

.

Abs.

Wavelength / nm

365nm-stable

450nm-stable

Figure S21. UVVis spectral change of Eu(LA)3 in PMMA film (5.0wt%) upon irradiation at 365 nm (a) and recoverable irradiation at 450 nm (b) (Inset: reversible change of absorption intensity at 358 nm in the photostationary states after alternating irradiation at andnm in repeated switching cycles).

250 300 350 400 450 500 550 600 6500.00

0.05

0.10

0.15

0.20

0.25

0 5 10 15 20

0.17

0.18

0.19

0.20

0.21

0.22

Cycle numbers

Abs

.Abs.

Wavelength / nm

365nm-stable450nm-stable

Figure S22. UVVis spectral change of Gd(LA)3 in PMMA film (5.0wt%) upon irradiation at 365 nm (a) and recoverable irradiationat 450 nm (b) (Inset: reversible change of absorption intensity at 358 nm in the photostationary states after alternating irradiation at andnm in repeated switching cycles).

-20 0 20 40 60 80 100 120 140 160 180 200

0

1

2

3

4

5

6

7

ln

[(A

-A0/

A -A

t)]

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0.35632

Adj. R-Square 0.98361Value Standard Error

N Intercept 0.40608 0.17348N Slope 0.00321 1.87563E-4

LA in acetonitrile

0 10 20 30 40 50 60-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*xWeight No WeightinResidual Sum of Squares

0.02875

Adj. R-Square 0.96794Value Standard Erro

I Intercept -0.0482 0.06052I Slope 0.02196 0.00199

LA in ethanol

0 50 100 150 200 250 300

0.0

0.5

1.0

1.5

2.0

2.5

3.0

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*xWeight No WeightingResidual Sum of Squares

0.05916

Adj. R-Square 0.98373Value Standard Error

I Intercept 0.10257 0.07507I Slope 0.00854 5.48297E-4

LA in hexane

13

Figure S23. The trans-cis photoisomerization kinetics of ln(A∞−A0)/(A∞−At) as a function of time for

LA in different solvents.

0 20 40 60 80 100 120

0.00

0.05

0.10

0.15

0.20

0.25

0.30 LB in Acetonitrile

ln[(A

-A

0/A

-At)]

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

6.59734E-4

Adj. R-Square 0.97555Value Standard Error

E Intercept 0.01402 0.01407

E Slope 0.00212 2.04665E-4

time (s)

Figure S24. The trans-cis photoisomerization kinetics of ln(A∞−A0)/(A∞−At) as a function of time for LB in acetonitrile.

Figure S25. The trans-cis photoisomerization kinetics of ln(A∞−A0)/( (A∞−At)) as a function of time for La(LA)3 in different solvents.

Figure S26. The trans-cis photoisomerization kinetics of ln(A∞−A0)/( (A∞−At)) as a function of time for Eu(LA)3 in different solvents.

0 50 100 150 200 250 300

0.0

0.5

1.0

1.5

2.0

2.5

3.0

ln[(A

-A

0/A

-At)]

Gd(LA)3 in acetonitrile

time (s)

Equation y = a + b*x

Weight No WeightingResidual Sum of Squares

0.04688

Adj. R-Square 0.9878Value Standard Error

H Intercept 0.10799 0.05668H Slope 0.00849 4.21649E-4

0 50 100 150 200 250 3001.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

ln[(A

-A

0/A

-At)]

Gd(LA)3 in ethanol

time (s)

Equation y = a + b*xWeight No WeightingResidual Sum of Squares

0.04722

Adj. R-Square 0.9894Value Standard Error

G Intercept 1.98624 0.05623G Slope 0.00906 4.18875E-4

0 50 100 150 200 250 300

0.0

0.5

1.0

1.5

2.0

2.5

3.0

ln[(A

-A

0/A

-At)]

Gd(LA)3 in hexane

time (s)

Equation y = a + b*xWeight No WeightinResidual Sum of Squares

0.01289

Adj. R-Square 0.99671Value Standard Erro

H Intercept -0.0124 0.02938H Slope 0.00852 2.18838E-4

0 10 20 30 40 50 60-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7 Eu(LA)3 in acetonitrile

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*x

Weight No Weightin

Residual Sum of Squares

0.00368

Adj. R-Square 0.98346Value Standard Erro

H Intercept 0.04022 0.02166H Slope 0.01101 7.12328E-4

0 50 100 150 200 250 300

0.0

0.5

1.0

1.5

2.0

2.5

3.0

ln[(A

-A

0/A

-At)]

Eu(LA)3 in ethanol

time (s)

Equation y = a + b*xWeight No WeightinResidual Sum of Squares

0.02078

Adj. R-Square 0.99576Value Standard Erro

G Intercept 0.0538 0.03049G Slope 0.0091 2.44283E-4

0 50 100 150 200 250 300

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5 Eu(LA)3 in hexane

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*xAdj. R-Square 0.9817

Value Standard ErrorB Intercept 0.05342 0.12457B Slope 0.00561 9.98135E-4

0 10 20 30 40 50 60

0.0

0.2

0.4

0.6

0.8

1.0

1.2

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*xWeight No WeightingResidual Sum of Squares

0.02478

Adj. R-Square 0.9568Value Standard Error

H Intercept -0.02096 0.05618H Slope 0.01749 0.00185

La(LA)3 in acetonitrile

0 20 40 60 80 100 120-0.20.00.20.40.60.81.01.21.41.61.8 La(LA)3 in ethanol

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*xWeight No WeightingResidual Sum of Squares

0.00631

Adj. R-Square 0.99313Value Standard Error

H Intercept 0.04929 0.04352H Slope 0.0132 6.33065E-4

0 100 200 300 400 500 600

0

1

2

3

4

5

ln[(A

-A

0/A

-At)]

La(LA)3 in hexane

time (s)

Equation y = a + b*xWeight No WeightinResidual Sum of Squares

0.03055

Adj. R-Square 0.99725Value Standard Erro

G Intercept 0.08214 0.05408G Slope 0.00753 1.97397E-4

14

Figure S27. The trans-cis photoisomerization kinetics of ln(A∞−A0)/( (A∞−At)) as a function of time for Gd(LA)3 in different solvents.

Figure S28. The trans-cis photoisomerization kinetics of ln(A∞−A0)/( (A∞−At)) as a function of time for Yb(LA)3 in different solvents.

-200 0 200 400 600 800 100012001400160018002000

0.00

0.05

0.10

0.15

0.20

0.25

0.30 La(LB)3 in hexane

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0.00161

Adj. R-Square 0.96586Value Standard Error

K Intercept 0.01704 0.01034

K Slope 1.37432E-4 1.31477E-5

Figure S29. The trans-cis photoisomerization kinetics of ln(A∞−A0)/( (A∞−At)) as a function of time for La(LB)3 in hexane solution.

Figure S30. The trans-cis photoisomerization kinetics of ln(A∞−A0)/( (A∞−At)) as a function of time for Eu(LB)3 in different solvents.

0 20 40 60 80 100 120

0.0

0.1

0.2

0.3

0.4

0.5

ln[(A

-A

0/A

-At)]

Eu(LB)3 in acetonitrile

time (s)

Equation y = a + b*x

Weight No WeightingResidual Sum of Squares

0.00324

Adj. R-Square 0.96325Value Standard Error

I Intercept 0.02707 0.02031I Slope 0.00344 3.33955E-4

0 10 20 30 40 50 60

0.0

0.1

0.2

0.3

0.4

0.5

0.6 Eu(LB)3 in ethanol

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0.00514

Adj. R-Square 0.96254Value Standard Error

I Intercept 0.01875 0.02469

I Slope 0.00872 8.59718E-4

0 10 20 30 40 50 60

0.0

0.5

1.0

1.5

2.0

ln[(A

-A

0/A

-At)]

Eu(LB)3 in hexane

time (s)

Equation y = a + b*x

Weight No WeightingResidual Sum of Squares

0.07053

Adj. R-Square 0.95516Value Standard Error

J Intercept 0.14554 0.0979J Slope 0.02949 0.00218

0 20 40 60 80 100 120

0.0

0.2

0.4

0.6

0.8

1.0

1.2

ln[(A

-A

0/A

-At)]

Yb(LA)3 in acetonitrile

time (s)

Equation y = a + b*xWeight No WeightingResidual Sum of Squares

0.00108

Adj. R-Square 0.99868Value Standard Error

G Intercept 0.0096 0.00899G Slope 0.00981 1.59569E-4

0 50 100 150 200 250 300

0.0

0.5

1.0

1.5

2.0

2.5

3.0 Yb(LA)3 in ethanol

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*xWeight No WeightingResidual Sum of Squares

0.0192

Adj. R-Square 0.99598Value Standard Error

G Intercept 0.0595 0.0293G Slope 0.00905 2.34778E-4

0 20 40 60 80 100 120

0.0

0.2

0.4

0.6

0.8

1.0

1.2

ln[(A

-A

0/A

-At)]

Yb(LA)3 in hexane

time (s)

Equation y = a + b*xWeight No WeightinResidual Sum of Squares

0.00538

Adj. R-Square 0.99256Value Standard Err

H Intercept 0.0397 0.02006H Slope 0.0092 3.56267E-4

0 200 400 600 800 1000 1200

0.0

0.2

0.4

0.6

0.8

1.0 Gd(LB)3 in acetonitrile

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0.02909

Adj. R-Square 0.9602Value Standard Error

F Intercept 0.0851 0.03595F Slope 7.42718E-4 6.91151E-5

0 10 20 30 40 50 60

0.0

0.2

0.4

0.6

0.8

1.0 Gd(LB)3 in ethanol

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*x

Weight No WeightingResidual Sum of Squares

0.00263

Adj. R-Square 0.99191Value Standard Error

F Intercept 0.03956 0.02296F Slope 0.01445 7.52517E-4

0 5 10 15 20 25 30-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

ln[(A

-A

0/A

-At)]

Gd(LB)3 in hexane

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0.0175

Adj. R-Square 0.96213Value Standard Error

F Intercept 0.08129 0.03912

F Slope 0.02116 0.00254

15

Figure S31. The trans-cis photoisomerization kinetics of ln(A∞−A0)/( (A∞−At)) as a function of time for Gd(LB)3 in different solvents.

Figure S32. The trans-cis photoisomerization kinetics of ln(A∞−A0)/( (A∞−At)) as a function of time for Yb(LB)3 in different solvents.

Figure S33. The trans-cis photoisomerization kinetics of ln(A∞−A0)/( (A∞−At)) as a function of time for La(LA)3, Eu(LA)3, Gd(LA)3 and Yb(LA)3 in PMMA film.

0 10 20 30 40 50 60

0.0

0.1

0.2

0.3

0.4

0.5 Yb(LB)3 in acetontrile

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0.00634

Adj. R-Square 0.96612Value Standard Error

F Intercept 0.05265 0.04166F Slope 0.0067 0.00123

0 50 100 150 200 250 300

0.0

0.5

1.0

1.5

2.0

2.5

3.0ln

[(A

-A0/

A -A

t)]Yb(LB)3 in ethanol

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0.40568

Adj. R-Square 0.96576Value Standard Error

F Intercept 0.28313 0.16867F Slope 0.0083 0.00125

0 20 40 60 80 100 120

0.00

0.05

0.10

0.15

0.20

0.25

0.30Yb(LB)3 in hexane

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*x

Weight No WeightingResidual Sum of Squares

0.00377

Adj. R-Square 0.97891Value Standard Error

F Intercept 0.04472 0.02265F Slope 0.0022 3.67429E-4

0 20 40 60 80 100 120-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

ln[(A

-A

0/A

-At)]

La(LA)3 in PMMA

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0.01658

Adj. R-Square 0.99631Value Standard Error

E Intercept 0.0927 0.06281

E Slope 0.00486 9.35667E-4

0 20 40 60 80 100 120

0.0

0.2

0.4

0.6

0.8

1.0

ln[(A

-A

0/A

-At)]

Eu(LA)3 in PMMA

time (s)

Equation y = a + b*x

Weight No WeightingResidual Sum of Squares

0.01155

Adj. R-Square 0.96561Value Standard Error

E Intercept 0.08138 0.04874E Slope 0.00621 7.87378E-4

0 20 40 60 80 100 120

0.0

0.1

0.2

0.3

0.4

0.5

ln[(A

-A

0/A

-At)]

Gd(LA)3 in PMMA

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

0.00199

Adj. R-Square 0.98336Value Standard Error

E Intercept 0.03425 0.02024E Slope 0.00334 3.26974E-4

0 20 40 60 80 100 120

0.0

0.1

0.2

0.3

0.4Yb(LA)3 in PMMA

ln[(A

-A

0/A

-At)]

time (s)

Equation y = a + b*x

Weight No Weighting

Residual Sum of Squares

1.77027E-4

Adj. R-Square 0.99603Value Standard Error

F Intercept -0.00783 0.01076

F Slope 0.00338 1.50651E-4

16

Figure S34. 1H NMR spectrum of A compound in CDCl3.

Figure S35. 1H NMR spectrum of LA ligand in CDCl3.

Figure S36. 1H NMR spectrum of B compound in CDCl3.

17

Figure S37. 1H NMR spectrum of LB ligand in CDCl3.

Figure S38. 1H NMR spectrum of complex La(LA)3 in CDCl3.

Figure S39. 1H NMR spectrum of complex Eu(LA)3 in DMSO-d6.

18

Figure S40. 1H NMR spectrum of complex Yb(LA)3 in CDCl3.

Figure S41. 1H NMR spectrum of complex La(LB)3 in DMSO-d6.

19

Figure S42. 1H NMR spectrum of complex Eu(LB)3 in CDCl3.

Figure S43. 1H NMR spectrum of complex Yb(LB)3 in CDCl3.

20

Figure S44. IR spectrum of LA ligand in KBr pellet.

Figure S45 IR spectrum of complex La(LA)3 in KBr pellet.

Figure S46. IR spectrum of complex Eu(LA)3 in KBr pellet.

21

Figure S47. IR spectrum of complex Gd(LA)3 in KBr pellet.

Figure S48. IR spectrum of complex Yb(LA)3 in KBr pellet.

Figure S49. IR spectrum of complex LB ligand in KBr pellet.

22

Figure S50. IR spectrum of complex La(LB)3 in KBr pellet.

Figure S51. IR spectrum of complex Eu(LB)3 in KBr pellet.

Figure S52. IR spectrum of complex Gd(LB)3 in KBr pellet.

23

Figure S53. IR spectrum of complex Yb(LB)3 in KBr pellet.