Electronic supplementary information Photoinduced Intramolecular

Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2013

1

Electronic supplementary information

Photoinduced Intramolecular Energy Transfer and Anion Sensing Studies of Isomeric RuIIOsII Complexes Derived from an Asymmetric Phenanthroline-Terpyridine Bridge

Dinesh Maity, Chanchal Bhaumik, Debiprasad Mondal and Sujoy Baitalik*

Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata – 700032, India


2 Table S1 Photophysical data of 1-3 in different solvents Solvents

Com poun ds

Luminescence

Absorption max/ nm ( / M-1cm-1)

E0-0 / (eV)

CH2Cl2

1 2 3

461(12920), 428(sh)(10470) 650(br)(4190), 486(20590), 438(sh)(19700) 501(19750), 406(11080)

max / nm 600 707 647

CH3OH

1 2 3

459(19290), 424(sh)(14760) 650(br)(5370), 484(26030), 434(sh)(23900) 498(44830)

607 717 656

432 83.08 6.80

206 41.01 1.14, 3.00

2.31 1.86 2.20

(CH3)2CO

1 2 3

460(20160), 424(sh)(15730) 653(br)(4260), 487(20000), 437(sh)(18820) 503(51160)

611 720 660

408 70.79 8.96

192 41.54 2.60, 4.80

2.30 1.85 2.17

CH3CN

1 2 3

460(17240), 426(sh)(13860) 650(br)(5600), 486(26000), 435(sh)(24000) 500(46420)

607 720 658

297 83.15 6.90

151 44.31 1.79, 3.34

2.30 1.85 2.17

H2O

1 2 3

464(17550), 428(14380) 665(br)(3230), 487(17870), 436(sh)(17570) ---

610 723 --

579 32.57 --

542 39.20 --

2.28 1.85 --

DMSO

1 2 3

464(18000), 429(sh)(14630) 665(br)(2790), 490(13900), 438(sh)(16320) 508(63420)

620 756 667

576 22.01 21.36

353 43.57 3.11, 14.12

2.26 1.81 2.15

 / ns

Φ/ 10-3 497 237 34.92

426 92.06 1.12, 30.09

2.31 1.87 2.22


3

Table S2 Spectroscopic and relevant photophysical data for intramolecular energy transfer in 4 and 5 in different solvents Solvents

CH2Cl2

Com poun ds 4 5

CH3OH

4 5

(CH3)2CO

4 5

CH3CN

4 5

H2O

4 5

DMSO

Luminescence -3 max / Φ / 10  / ns nm 747 216 168

E0-0 / eV

ΔG0 / eV

1.81

-0.50

710

135

71.84

1.90

-0.32

672(br)(8560), 494(52540), 464(sh)(44750), 422(sh)(33390) 666(3980), 496(74660)

743

157

107

1.82

-0.49

722

73.07

39.20

1.89

-0.28

672(br)(6440), 495(35000), 466(sh)(32370), 427(sh)(24580) 669(br)(4740), 496(74580), 438(br)(36020)

753

154

120

1.80

-0.50

725

75.37

40.54

1.88

-0.29

750

164

101

1.81

-0.49

722

82.26

42.52

1.88

-0.29

749

84.73

89.79

1.87

-0.41

724

31.80

31.85

1.87

---

Absorption max/ nm ( / M-1cm-1) 674(br)(4300), 495(26600), 465(sh)(25300), 429(sh)(17400) 665(br)(3200), 496(50200), 440(br)(25000)

672(br)(8700), 494(45600), 460(sh)(37100), 424(sh)(26600) 658(br)(4180), 494(66560), 439(br)(32460) 671(br)(5200), 491(33600), 465(br)(30500) 667(br)(2100), 495(34600), 437(br)(16400)

4

680(br)(7370), 508(43640), 470(br)(34240), 427(sh)(31950)

757

195

151

1.79

-0.47

5

674(br)(3220), 507(53980), 440(sh)(29830)

762

21.93

38.16

1.80

-0.35


4

4

N

7

3'

N

3'

7

8

H N

9

11

6

3

3"

5'

N N

4'

N

N N

5

10

6

N 8

5

3

N

6'

N

N

4

Scheme S1. Proton numbering of tpy-PhCH3, phen-Hbzim-tpy, and bpy.


5

100

515.59

515.59 514.59

%

514.09

516.09

50 513 514 515 516 517 m/z 1130.03

0 400

600

800 1000 1200 m/ z

Fig. S1 ESI-MS (positive) for the complex cations [(bpy)2Os(phen-Hbzim-tpy)]2+ (m/z = 515.59) and [(bpy)2Os(phen-bzim-tpy)]+ (m/z = 1130.03) in acetonitrile showing the observed and isotopic distribution patterns.


6

476.37

m/z Fig. S2 ESI-MS (positive) for the complex [(tpy–PhCH3)Ru(tpy-Hbzim-phen)]2+ (m/z = 476.37) in acetonitrile.


7

100

484.92

100

(a)

363.65 363.90 363.39 364.14

484.26

% 483

484.19

485.19 485.52

485.25

50 482

484.52

484.92

483.92

%

484.52

(b)

484

485

486

50

362 363 364 365 366 m/z

363.65

482 483 484 485 486 487 m/z

487

m/z

400

500

600 m/z

700

0 800 0

200 400 600 800 1000 m/z

Fig. S3 ESI-MS (positive) for the complex cations, (a) [(bpy)2Ru(phen-bzim-tpy)Os(tpy– PhCH3)]3+ (m/z = 484.92) (b) [(bpy)2Os(phen-Hbzim-tpy)Ru(tpy–PhCH3)]4+ (m/z = 365.65) and [(bpy)2Os(phen-bzim-tpy)Ru(tpy–PhCH3))]3+ (m/z = 484.52) in acetonitrile showing the observed and isotopic distribution patterns.


8

5

4

N

N

N 8

7

3'

7

H N

8

11 5'

N

6'

N

3

3"

4'

N

N

6

H(3') H(3')

3'

9

N N

5

10

6

3

N

N

4

H(4)+H(4')

H(6)

H(3)+H(6')+H(7) + H(10)+H(11)

H(5)+H(5')

H H H (3'') (8) (7) H(9)

H(4') H(6')

H(8)

5 H(3') H(3')

H(6)+H(9) H(3'') H(7)+H(8)

H(5')+H(10) H(4') + + H(11) H H H(4)+H(4') H(6') H (7) (3) (5') H(6') H(8) H(4)

H (5)

4 H(7)+H(8)

H(3)+H(7) H(3') H(3') H(6)

H(9)

H (11) H (10)

H(4)

H(8)

H(5)

3 H(3')+H(3'')+H(6)+H(9) H(4') + H(11) H(3'')

H(8)

H(3)

H(7) H(4)

H(5') + H H(6') H (6') H(5) (4')

H(5')

2 H(3')+H(3'')+H(6)+H(9)

H(3)

H(3'')

1 1 0 .0

9 .5

9 .0

H(8)

H(4')+H(10) + H(5)+H(5') H(11) + H H(6) H(7) (4) H(6') H(4')

8 .5 ppm

8 .0

Fig. S4 1H NMR spectra of 1–5 in DMSO-d6 at room temperature.

7 .5

H(5')

7 .0


9

2.4 CH2Cl2 CH3OH CH3CN DMSO H2O

1.2

800 PL Int(a.u.)

Abs

(a)

(b)

CH2Cl2 CH3OH CH3CN DMSO H2O

600 400 200

0.0

300

400 /nm

500

600

0

600

720 /nm

Fig. S5 (a) Absorption and (b) photoluminescence spectra of 1 in different solvents.

840


10

640 CH2Cl2 CH3OH CH3CN DMSO H2O

(a)

Abs

1.6

(b)

PL Int(a.u.)

2.4

0.8 0.0

300

450

/nm

600

750


320

0

640

720

/nm

800


880


11

2

600

1

0

400

(b)


/nm

600

PL Int(a.u.)

Abs

(a)

800


300

0 640

720

/nm

800


880


12

340

2

1

0

400

/nm

600

(b)

PL Int(a.u.)

Abs

(a)


800


170

0

640

720 800 /nm


880


13

(c)

(b)

(a)

0 .0

0 .6 1 .2 P o ten tial(E / V )

1 .8

Fig. S9 Cyclic voltammograms of 1 (a), 2 (b), and 3 (c) in acetonitrile at room temperature showing the oxidation of the complexes.


14

(e)

(d)

(c)

(b)

(a) 0 .0

-0 .6

-1 .2

-1 .8

-2 .4

P o te n tia l(E /V )

Fig. S10 Square wave voltammograms of 1 (a), 2 (b), 3 (c), 4 (d), and 5(e) in acetonitrile at room temperature showing the reduction of the complexes.


15

/ns

Counts(Log)

1000

CH2Cl2 CH3OH (CH3)2CO CH3CN DMSO H2O

100

426.00 206.00 192.00 151.00 353.00 542.00

10 0

1500

3000 /ns

4500

Fig. S11 Time–resolved photoluminescence decays of 1 in different solvents at room temperature. Lifetimes of the complex in different solvents are also given in the figure.


16

/ns

Counts(Log)

1000


100

92.06 41.01 41.54 44.31 43.57 39.20

10 0

350 /ns

700



17

/ns /ns

Counts(Log)

1000

CH2Cl2 CH3OH (CH3)2CO CH3CN DMSO

1.12 1.14 2.60 1.79 3.11

30.09 3.00 4.80 3.34 14.12

100

10 0

55 /ns

110



18

/ns

Counts(Log)

1000

CH2Cl2 CH3OH (CH3)2CO CH3CN

DMSO H2O

100

168.00 107.00 120.00 101.00 151.00 89.79

10 0

500 /ns

1000



19

/ns

Counts(Log)

1000


100

71.84 39.20 40.54 42.52 38.16 31.85

10 0

200

/ns

400

600



20

0.40 0.35

-1

0.30 0.25

Abs

6

K= (2.96 ± 0.15)×10 M

1.5

200

0.45

0.0

1.0

-6

-5

9.0x10 1.8x10 2.7x10 [CN ] / [mol/L]

-5

PL Int(a.u.)

(a)

Abs405 nm

2.0

(c) PL Int722 nm

200 0.50

150

50 0.0

-6

-5

9.0x10 1.8x10 2.7x10 [CN ] / [mol/L]

-5

100

0.50

210

0.35 6

-1

K= (2.81 ± 0.12)×10 M

0.30 0.25

0.0

-5

-5

-5

1.0x10 2.0x10 3.0x10 [F ] / [mol/L]

PL Int(a.u.)

0.40

160

6

-1

K= (2.84 ± 0.08)×10 M

140

70 0.0

-5

-5

-5

1.0x10 2.0x10 3.0x10 [F ] / [mol/L]

80

0

300 400 500 600 700 /nm

PL Int 719 nm

(d)

0.45 Abs403 nm

(b) Abs

100

240

2.4

0.0

-1

K= (3.12 ± 0.18)×10 M

50

0.5

1.2

6

150

640

720

800

880

/nm

Fig. S16 Changes in UV–vis absorption and luminescence spectra of 5 in acetonitrile solution (2.0 × 10-5 M) upon incremental addition of CN- (a and c, respectively) and F- (b and d, respectively) ions (5.0 × 10-3 M). The insets show the fit of the experimental absorbance (a and b) and luminescence (c and d) data to a 1:1 binding profile.


21

560 Abs 405nm

Abs

0.8

0.28 6

-1

K= (3.17 ± 0.17)×10 M

0.24 0.0

-6

-5

9.0x10- 1.8x10 2.7x10 [AcO ] / [mol/L]

-5

560

(b)

PL Int 750 nm

(a)

0.32

PL Int(a.u.)

1.2

520

480

440

6

-1

K= (3.08 ± 0.19)×10 M

0.0

280

-6

-5

-5

9.0x10 1.8x10 2.7x10 [AcO ] / [mol/L]

0.4

0.0

400

600

800

0

640

720

800

880

Fig. S17 Changes in UV–vis absorption and luminescence spectra of 4 in acetonitrile solution (2.0 × 10-5 M) upon incremental addition of AcO- ion (5.0 × 10-3 M). The insets show the fit of the experimental absorbance and luminescence data to a 1:1 binding profile.


22

200

0.40 0.35

6

K= (2.71 ± 0.07)×10 M

-1

0.30 0.0

1.1

200

(b)

0.45

-5

-5

1.0x10 2.0x10 3.0x10 [AcO ] / [mol/L]

-5

PL Int(a.u.)

Abs

(a)

Abs407 nm

0.50

PL Int 722 nm

2.2

150

6

150

-1

K= (2.70 ± 0.08)×10 M

100 50 0.0

-5

-5

-5

1.0x10 2.0x10 3.0x10 [AcO ] / [mol/L]

100 50

0.0

300 400 500 600 700

0

640

720

800

880

Fig. S18 Changes in UV–vis absorption and luminescence spectra of 5 in acetonitrile solution (2.0 × 10-5 M) upon incremental addition of AcO- ion (5.0 × 10-3 M). The insets show the fit of the experimental absorbance and luminescence data to a 1:1 binding profile.


23

0.0

0.3

0.6 0.0

400

520

0.8

0.6

1.2

(b) PL Int(a.u.)750 nm

1.0

600 /nm

0.6 0.9 Equiv.OH

1.2

PL Int(a.u.)

1.8 Abs

550

(a) Abs520 nm

2.4

800

500 480 460 440 0.0

275

0 640

720

0.3

0.6 0.9 Equiv.OH

800

/nm

Fig. S19 Changes in UV–vis absorption and luminescence spectra of 4 in acetonitrile solution (2.0 × 10-5 M) upon incremental addition of OH- ion (5.0 × 10-3 M). The insets show the change of absorbance and luminescence with equivalent of OH- ion.

1.2

880


24

220

(a)

(b)

Abs

Abs520 nm

0.64

1.1

0.56 0.48 0.40 0.0

0.3

0.6 0.9 Equiv. OH

1.2

PL Int(a.u.)

0.72

220 PL Int(a.u.) 720 nm

2.2

165

165 110 55

110

0.0

0.3

0.6 0.9 Equiv.OH

1.2

55

0.0

400

/nm

600

800

0

640

720

800 /nm

Fig. S20 Changes in UV–vis absorption and luminescence spectra of 5 in acetonitrile solution (2.0 × 10-5 M) upon incremental addition of OH- ion (5.0 × 10-3 M). The insets show the change of absorbance and luminescence with equivalent of OH- ion.

880


25

0.6

380

(a)

0.3

0.0 300

0.00

375

3

-1

K= (7.38 ± 0.42)×10 M

0.0

-3

-3

2.0x10 1.0x10 [AcO ] / [mol/L]

450 /nm

525

(b)

400 PL Int 460 nm

0.11

PL Int(a.u)

Abs

Abs415 nm

0.22

190

0

300 3

200 100

420

0.0

-4

-3

1.8x10 9.0x10 [AcO ] / [mol/L]

490 560 /nm

Fig. S21 Changes in UV–vis absorption (a) and luminescence (b) spectra of phenHbzim-tpy in dimethylsulfoxide solution (2.0 × 10-5 M) upon incremental addition of AcO- ion. The insets show the fit of the experimental absorbance and luminescence data to a 1:1 binding profile.

-1

K= (6.93 ± 0.22)×10 M

630


26

0.6

340 (b)

(a) 0.26

3

-1

K= (3.25 ± 0.23)×10 M

0.3

0.00

-3

0.0

6.0x10

-2

1.2x10

-

[H2PO4 ] / [mol/L]

0.0 300

375

/nm

450

525

PL Int460 nm

0.13

PL Int(a.u.)

Abs

Abs420 nm

340

170

255 3

85 0.0

0

440

-3

-2

6.0x10 1.2x10 [H2PO4 ] / [mol/L]

550 /nm

Fig. S22 Changes in UV–vis absorption (a) and luminescence (b) spectra of phenHbzim-tpy in dimethylsulfoxide solution (2.0 × 10-5 M) upon incremental addition of H2PO4- ion. The insets show the fit of the experimental absorbance and luminescence data to a 1:1 binding profile.

-1

K= (1.95 ± 0.11)×10 M

170

660


27

0.6

(a)

340 (b)

0.42

0.00

0.3

0.0 300

375

/nm

0

5 10 15 20 25 Equiv.OH

450

525

PL Int(a.u)

0.21

PL Int(a.u.)

Abs

Abs 400 nm

360

170

0

240

120

0

420

5

10 15 20 25 Equiv.OH

490 560 /nm

Fig. S23 Changes in UV–vis absorption and luminescence spectra of phen-Hbzim-tpy in acetonitrile solution (2.0 × 10-5 M) upon incremental addition of OH- ion. The insets show the change of absorbance and luminescence with equivalent of OH- ion.

630


28

/ns

Counts(Log)

1000

F

-

100

free 0.25 eq 0.50 eq 0.75 eq 1.0 eq

101.00 103.73 105.74 107.20 107.70

10 0

300

600 /ns

900

Fig. S24 Change in time-resolved luminescence decay of 4 in acetonitrile (2.0 × 10−5 M) at room temperature upon incremental addition of F− ion (5.0 × 10−3 M). Insets show the lifetimes of the complex.


29

/ns

Counts(Log)

1000

F

-

free 0.25 eq 0.50 eq 0.75 eq 1.0 eq

100

42.52 36.81 29.61 27.02 26.08

10 0

100

200 /ns

300

400

Fig. S25 Change in time-resolved luminescence decay of 5 in acetonitrile solution (2.0 × 10−5 M) at room temperature upon incremental addition of F− ion (5.0 × 10−3 M). Insets show the lifetimes of the complex.


30

H(10) + H(11)

H(7) NH

1.0eq

0.8eq

0.6eq

0.4eq

Free 15.0

14.5

14.0 1 0 . 0

9 .5

9 .0

8 .5

8 .0

7 .5

Fig. S26 1H NMR titration of sensor 4 in DMSO-d6 solution (5.0 × 10−3 M) upon addition of F- ion (1.25 × 10−1 M, 0–1 equivalents).

7 .0


31

600 0.52

0.26 pK = 10.39

6

0.0

300

400 /nm

8

10 pH

12

14

500

PL Int(a.u)

Abs

600

0.39

0.13

0.4

(b) PL Int 470 nm

(a) Abs380 nm

0.8

400

400 200 0

6

200

0

440

8

10 pH

550 /nm

Fig. S27 Changes in UV–vis absorption (a) and luminescence (b) spectra of phenHbzim-tpy with variation of pH in dimethylsulfoxide-water (3:2 v/v). The insets show the changes of absorbance and luminescence intensities with the variation of pH.

12

14

660


32

113 1000

/ns

112

Counts(Log)

pH(2-12)

100

111

10 0

250

500

750

1000

/ns

110 *

pK =8.20

109 3

6 pH

9

12

Fig. S28 Change of the luminescence lifetimes of 4 with variation of pH in acetonitrilewater (3:2 v/v). Inset shows the decay profiles of 4 as a function of pH. Excited state pK* is also given in figure.


33

50

/ns

Counts(Log)

1000

100

40

30

pH(2-12)

10 0

200

400

 /ns

*

pK = 7.96

3

6 pH

9

12

Fig. S29 Change of the luminescence lifetimes of 5 with variation of pH in acetonitrilewater (3:2). Inset shows the decay profiles of 5 as a function of pH. Excited state pK* is also given in figure.


34

2.04 *

1.98

1.92

Counts(log)

/ns

pK = 10.40

pH= 2.5-14

1000 100 10 8

1.86

6

16

/ns

8

24

10 pH

12

14

Fig. S30 Change of the luminescence lifetimes of phen-Hbzim-tpy with variation of pH in dimethylsulfoxide -water (3:2). Inset shows the decay profiles of phen-Hbzim-tpy as a function of pH. Excited state pK* is also given in figure.