Zinc(II) tetraphenyltetrabenzoporphyrin complex as triplet ...S1 Electronic Supplementary...

S1

Electronic Supplementary Information for

Zinc(II) tetraphenyltetrabenzoporphyrin complex as

triplet photosensitizer for triplet-triplet annihilation

upconversion

Xiaoneng Cui, Jianzhang Zhao,* Pei Yang and Jifu Sun

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of

Technology, E-208 West Campus, 2 Ling-Gong Road, Dalian 116024, P. R. China.

E-mail : [email protected]

Web : http://finechem.dlut.edu.cn/photochem

General information………… ……… …………… …… ………………….……… ……… …………S2

Synthesis of compound Zn TPTBP, H2 TPTBP, Pd TPTBP and A-1………...………… ……… …………S3

Fig. S1-S2 NMR spectra of ZnTPTBP and MS of ZnTPTBP………… ……… ..…………… ………S5

Fig. S3-S4 NMR spectra of H2TPTBP and MS of H2TPTBP…………. ……. …… ………………… S6

Fig. S5-S6 NMR spectra of PdTPTBP and MS of PdTPTBP………………… ………………… …S7

Fig. S7-S8 NMR and MS spectra of A-1………… ……… ………………………………… ……S8

Fig. S9-S12 77 K emission spectra and Luminescence spectra in N2……………… ……… ……S10

Fig. S13-S16 Transient absorption spectra………… ……… ……...……………...………………S11

Fig. S17-S22 Delayed fluorescence……… ……… ……………………… ………… … ………S13

Fig. S23-S24 Upconversion details of H2TPTBP and PdTPTBP……………..……...……………… S15

Fig. S25 Stern Volmer Plot for the quenching of the lifetime ……………….....………………… S17

Fig. S26 Time-resolved emission spectra (TRES) of H2TPTBP………………….………………… S18

Fig. S27 Time-resolved emission spectra (TRES) of PdTPTBP…………………..….………………… S19

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

S2

1. Experimental Section

General information

All the chemicals used in synthesis are analytical pure and were used as received. Solvents were dried and

distilled before used for synthesis. 1H and 13C NMR spectra were recorded on a 400 MHz Varian Unity Inova

spectrometer (TMS as the standard of the chemical shifts). The mass spectra were measured by a MALDI and ESI

Micro MS spectrometer. UV-vis absorption spectra were taken on a HP8453 UV-visible spectrophotometer.

Photoluminescence spectra were recorded on a Shimadzu RF 5301PC spectrofluorometer. Luminescence lifetimes

were measured on a OB 920 fluorescence/phosphorescence lifetime instrument. The nanosecond time-resolved

transient difference absorption spectra were detected by Edinburgh LP920 instruments (Edinburgh Instruments,

UK). The signal was buffered on a Tektronix TDS 3012B oscilloscope and was analyzed by the LP900 software.

Fluorescence quantum yields were measured with DCM (4-dicyanomethylene-6-(p-dimethylaminostyryl)-2-methyl-

4H-pyran) as the standard (ΦF = 0.1 in CH2Cl2).

A laser diode (continuous laser, 654 nm,12 mW, 95.5 mW cm-2) was used as the excitation source for the

upconversion. The power of the laser beam was measured with VLP-2000 pyroelectric laser power meter. For the

upconversion experiments, the mixed solution of the compound (triplet photosensitizers) and the triplet acceptors

was degassed with N2 for at least 15 min. The steady state upconverted fluorescence was recorded with a RF

5301PC spectrofluorometer. In order to repress the laser scattering, a small black box was put behind the

fluorescent cuvette as beam dump to trap the laser.

The upconversion quantum yields (ΦUC) of ZnTPTBP, H2TPTBP and PdTPTBP were determined with the prompt

fluorescence of the free porphyrin H2TPTBP as the inner standard, e.g. The upconversion quantum yields were

calculated with the following equation (Eq. 1), where ΦUC, Asam and Isam represents the quantum yield, absorbance,

integrated photoluminescence intensity and the refractive index of the samples. ηsam represents the diffraction

index used for the samples, symbols with ‘std’ stand the corresponding parameter for the standard (Eq. 1)

(Eq. 1)

The delayed fluorescence of the upconversion was measured with a nanosecond pulsed laser (OpoletteTM

355II+UV nanosecond pulsed laser, typical pulse length: 7 ns. Pulse repetition: 20 Hz. Peak OPO energy: 4 mJ. The

wavelength is tunable in the range of 210 – 355 nm and 410 – 2200 nm. OPOTEK, USA), which is synchronized to

FLS 920 spectrofluorometer (Edinburgh Instruments, UK). The pulsed laser is sufficient to sensitize the TTA

upconversion. The decay kinetics of the upconverted fluorescence (delayed fluorescence) was monitored with an

FLS920 spectrofluorometer (synchronized to the OPO nanosecond pulse laser). The prompt fluorescence lifetime of

the triplet acceptor A-1 was measured with EPL picosecond pulsed laser (405 nm, 405 ±10 nm, pulse width: 66.9 ps,

maximum average power: 5 mW; Edinburgh Instrument Ltd., UK) which was synchronized to the FLS 920

spectrofluorometer.

2

std sam samstd samsam std std

Φ 2Φ A IA I

ηη

⎛ ⎞⎛ ⎞⎛ ⎞= ⎜ ⎟⎜ ⎟⎜ ⎟

⎝ ⎠⎝ ⎠⎝ ⎠


S3

Synthesis of compounds ZnTPTBP, H2TPTBP, PdTPTBP and A-1

Scheme S1. Synthesis of meso-tetraphenyltetrabenzoporphyrin compounds of PdTPTBP, H2TPTBP, ZnTPTPB. The

molecular structure of triplet acceptor A-1 used in the TTA upconversion studies is also presented.

Zn TPTBP, H2 TPTBP and Pd TPTBP were synthesized according to a modified literature method.1

Synthesis of Zinc phenylacetate: Sodium hydroxide (2.32 g, 0.058 mol), phenylacetic acid (7.76 g, 0.058 mol) and

40 mL water were mixed together, the pH value was adjusted to 8.0. Then ZnCl2 (4.09 g, 0.03 mol) was dissolved in a

small amount of water and the pH value was adjusted to 3.0. With the exchange reaction between sodium

phenylacetate and ZnCl2, Zinc phenylacetate was obtained as a white precipitate. The product was isolated by

filtration and the product was used without further purification. Yield: 8.59 g (89.8%).

Synthesis of ZnTPTBP : The preparation followed a reported method.1 Under N2 atmosphere, phthalimide (1.47 g,

10.0 mmol), phenylacetic acid (1.80 g, 13.3 mmol) and Zinc phenylacetate (0.840 g, 2.5 mmol) were ground in a

mortar and loaded into a 50 mL round-bottom flask. The mixture was melted and stirred for 1 h at 360 °C until the

color turned dark green. The melt was collected and washed with water (2×100 mL) and dried over Na2SO4. The

product was dissolved in toluene and purified on column chromatography( Al2O3). The column was elutated firstly

with toluene/hexane (2:1, v/v) and then with toluene to remove the yellow and the red fractions. Finally, CH2Cl2

containing 1.5% tetrahydrofuran was used to elute the desired product. Yield: 405.0 mg (18.5 %). 1H NMR (DMSO-d6,

400 MHz): δ 8.27 (d, 8H, J = 7.2 Hz), 8.03 (d, 4H, J = 8.0 Hz), 7.96 (t, 8H, J = 16.0 Hz), 7.28−7.24 (m, 8H),

⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯

1. S. M. Borisov, I. Klimant, Dyes and Pigm. 2009, 83, 312−316.

NB

N

F F A-1

NH

O

O

COOH

Zn(PhAcO)2

N

N N

NZn

N

NH N

HN

CH2Cl2HCl

N

N N

NPd

Pd(OAc)2

CH2Cl2/DMF

Zn TPTBP H2 TPTBP

Pd TPTBP

360°C


S4

7.08−7.05 (m, 8H). MALDI-HRMS: Calcd ([C60H36N4Zn]+) m/z 876.22314, found m/z 876.2222. Other peaks: m/z

966.2708(ZnTPTBP+C7H7)) and m/z 1056.3065 (ZnTPTBP+2(C7H7)).1

Synthesis of H2TPTBP: The preparation followed a reported method.1 ZnTPTBP (50.0 mg, 0.057 mmol) was

dissolved in CH2Cl2 (20 mL) and then 15 mL of hydrochloride acid (HCl:H2O = 1:2, v/v) was added. The solution was

stirred for 30 min. Water (100 mL) was added in the mixture. The mixture was extracted with CH2Cl2 (3 × 30 mL). The

solvent was evaporated under reduced pressure, the solid was washed thoroughly with water and dried under

vacuum. The crude product was purified with column chromatography (silica gel, CH2Cl2) to give dark-green

powder. Yield: 22.3 mg (48.0 %) .1H NMR (400 MHz, DMSO-d6, ): δ 8.33 (d, 8H, J = 5.6 Hz ), 8.05 (t, 4H, J = 16.0 Hz ),

7.97 (t, 8H, J = 16.0 Hz), 7.33−7.00 (m, 16H), −1.07 (s, 2H). MALDI-HRMS: Calcd ([C60H38N4+H+]+), m/z 814.3097, found,

m/z 815.3129. Other peaks: m/z 905.3795(TPTBP+C7H7) and m/z 995.4377 (TPTBP+(C7H7)2).1

Synthesis of PdTPTBP: The preparation followed a reported method.1 Under nitrogen atmosphere, H2 TPTBP (30.3

mg, 0.037 mmol) was dissolved in 20 mL solution ( CH2Cl2:DMF = 1:3, v/v). Then Pd(OAc)2 (24.8 mg, 0.11 mmol) was

added. The reaction mixture was refluxed at 150 °C and stirred for 45 min until the UV-Vis absorption spectrum

indicated the reaction was finished. The weak absorption at 633 nm disappeared and a new strong absorption at

628 nm emerged. In toluene). After completion of the reaction, the mixture was cooled to r. t. The mixture was

evaporated to dryness under reduced pressure, then washed with hot water. The solid was dried under vacuum.

The product was dissolved in toluene and purified by column chromatography (Al2O3, toluene/hexane, 1:1, v/v).

Yield: 16.3 mg (47.9 %). 1H NMR ( 400 MHz. DMSO-d6): δ 8.25 (d, 8 H, J = 7.2 Hz), 8.04 (d, 4 H, J = 7.2 Hz), 7.97 (t, 8 H, J

= 14.0 Hz), 7.30−7.28 (m, 8 H), 7.06−7.03 (m, 8 H). MALDI-HRMS: Calcd ([C60H36N4Pd]+), m/z 918.1975, found, m/z

918.2038. Other peaks: m/z 1008.2810 (ZnTPTBP+C7H7) and m/z 1101.2496(ZnTPTBP+(C7H7)2).1

Synthesis of A-1 : A-1 were synthesized by a modified literature method.2 Orange power was obtained. Yield (28.0

mg, 51.2%). 1H NMR (CDCl3, 400 MHz): δ 8.28 (d, 2H, J = 7.6 Hz), 8.24 (d, 2H, J = 6.8 Hz), 7.73 (d, 3H, J = 7.6 Hz), 7.66 (d,

2H, J = 7.6 Hz), 7.53−7.42(m, 6H), 2.57 (s, 6H), 2.38 (q, 4H, J = 6.8 Hz), 1.48 (s, 6H), 1.04 (t, 6H, J = 14.4 Hz). EI-HRMS:

Calcd ([C43H37BN2F2]+), m/z 630.3018, found, m/z 630.3026.

⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯

2 A. Turshatov, D. Busko, Y. Avlasevich, T. Miteva, K. Landfester, S. Baluschev, ChemPhysChem. 2012, 13, 3112−3115.


S5

2. NMR and MS spectra

ppm

Fig. S1 1H NMR spectra of Zn TPTBP (400 MHz, DMSO-d6).

Fig. S2 MALDI-HRMS of ZnTPTBP.

m/z500 600 700 800 900 1000 1100 1200 1300 1400

%

0

10012121415 33 (1.100) Cn (Cen,4, 50.00, Ht); Sm (SG, 2x3.00); Sb (15,10.00 ); Cm (32:33)

1.25e3876.2222

856.6871522.0659

787.1327740.8444

878.2219

880.2179

966.2708967.2727

970.2668

971.26581056.30651060.3093

N

N N

NZn

N

N N

NZn

8.0 7.5 7.0

8.058.00 7.967.824.16

7.05

7.06

7.07

7.08

7.24

7.25

7.27

7.28

7.92

7.94

7.96

8.01

8.03

8.26

8.27

8 7 6 5 4 3 2 1 0

8.05 7.96

0.00

2.50

3.35

7.05

7.06

7.07

7.08

7.24

7.25

7.27

7.94

7.96

8.26

8.27


S6

ppm

Fig. S3 1H NMR spectra of H2TPTBP (400 MHz, DMSO-d6)

Fig. S4 MALDI-HRMS of H2TPTBP.

m/z500 600 700 800 900 1000 1100 1200 1300 1400

%

0


1.02e3815.3129

814.3085

512.0795

586.1387 813.3071613.1314

816.3195

905.3795906.3901

995.4377996.4348

1086.5464 1286.71071326.3225

N

NH N

HN

N

NH N

HN

8.0 7.5 7.0

8.098.038.00 7.974.07

7.00

7.07

7.14

7.21

7.33

7.93

7.95

7.97

8.01

8.03

8.05

8.31

8.33

8 7 6 5 4 3 2 1 0 -1

8.098.03 1.98

-1.0

7

2.51

3.31

7.07

7.14

7.21

7.33

7.93

7.95

7.97

8.03

8.31

8.33


S7

ppm

Fig. S5 1H NMR spectra of Pd TPTBP (400 MHz, DMSO-d6).

Fig. S6 MALDI-HRMS of Pd TPTBP.

( )

m/z500 600 700 800 900 1000 1100 1200 1300 1400

%

0


1.40e3918.2038

917.2078

916.2133829.1613

828.1548

827.1326748.1530543.9929

920.2122

921.2146

922.2195

923.21911008.28101010.29191011.36001013.3032

1101.2496

N

N N

NPd

N

N N

NPd

8.0 7.5 7.0

8.00 7.917.907.803.99

7.03

7.04

7.05

7.06

7.28

7.28

7.29

7.30

7.93

7.95

7.97

8.02

8.04

8.23

8.25

8 7 6 5 4 3 2 1 0

8.00 7.91

0.00

2.50

3.33

7.04

7.05

7.06

7.28

7.28

7.29

7.30

7.95

8.23

8.25


S8

ppm

Fig. S7 1H NMR spectra of A-1 (400 MHz, CDCl3).

Fig. S8 EI-HRMS of A-1.

NB

N

F F8.0 7.5

6.084.00 3.01 2.14

7.26

7.42

7.44

7.47

7.49

7.51

7.53

7.64

7.66

7.71

7.73

8.23

8.24

8.26

8.28

8 7 6 5 4 3 2 1 0

6.08 6.046.025.964.00

0.00

1.01

1.02

1.04

1.48

2.32

2.34

2.36

2.38

2.57

7.26

7.44

7.49

7.51

7.64

7.66

7.71

7.73

8.24

8.26

50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800m/z0

100

%

zjz121215-1 424 (7.067) Cm (424-77:85) TOF MS EI+ 2.93e3630.3026

615.2809

608.2815

307.6398282.1103163.067294.9979

595.2746385.0899 461.2060

631.3055

632.3065

634.3101716.7413

NB

N

F F


S9

Fig. S9 Emission spectra of ZnTPTBP, H2TPTBP and Pd TPTBP in ethanol-methanol (4:1, V/V) glass at

77 K. Excitation wavelength: 441 nm. c = 1.0 ×10-5 M.

Fig. S10 Emission spectra of ZnTPTBP in ethanol-methanol (4:1, v/v) glass at 77 K and in solution at

293 K. Excitation wavelength was 441 nm. c = 1.0 × 10-5 M. The asterisk indicated the

phosphorescence.

600 650 700 750 800 8500

40

80

120

Pd TPTBP

H2 TPTBP

Zn TPTBP

Inte

nsity

/ a.

u.

Wavelength / nm

650 700 750 800 8500

4

8

12

77 K 293 K

*

Inte

nsity

/ a.

u.

Wavelength / nm


S10

Fig. S11 Luminescence spectrum of the compounds H2 TPTBP in N2 or air-saturated solutions. λex =

441 nm. c = 1.0 × 10-5 M, in deaerated toluene. 20 °C.

Fig. S12 Luminescence spectra of (a) ZnTPTBP and (b) PdTPTBP λex = 441 nm. in N2 or air-saturated

toluene (1.0 × 10-5 M; 20 °C). The emission band in (b) at 638 nm is known.

600 660 720 780 8400

10

20

30

40

Air N2

Inte

nsity

/ a.

u.

Wavelength / nm

650 700 750 800 8500.0

2.0

4.0

6.0

8.0

Inte

nsity

Wavelength / nm

air N2

a

600 700 800 9000.0

3.0

6.0

9.0

12.0

Inte

nsity

Wavelength / nm

air N2

b


S11

Fig. S13 (a) Nanosecond time-resolved transient difference absorption spectra of ZnTPTBP, (b)

decay trace at 470 nm. Excited with 532 nm nanosecond pulsed laser excitation. In aerated toluene

(c = 1.0 ×10-5 M, 20 °C).

Fig. S14 (a) Nanosecond time-resolved transient difference absorption spectra of PdTPTBP, (b)

decay trace at 510 nm; Excited with 532 nm nanosecond pulsed laser excitation. In aerated toluene

(c = 1.0 ×10-5 M, 20 °C).

400 500 600 700

-0.10

-0.05

0.00

0.05

0.10a

4750 ns4500 ns ...... ...... 250 ns 0 ns

Wavelength / nm

2000 4000 6000 8000100000.00

0.03

0.06

0.09

0.12b

τ = 873 ns

Time / ns

400 500 600 700-0.15

-0.10

-0.05

0.00

0.05a

2400 ns2266 ns ...... ...... 133 ns 0 ns

Δ O

. D.

Wavelength / nm2500 5000 7500 10000-0.20

-0.15

-0.10

-0.05

0.00

0.05

τT = 505 ns

b

Δ O

. D.

Time / ns


S12

Fig. S15 (a) Nanosecond time-resolved transient difference absorption spectra of H2TPTBP, (b) decay

trace at 510 nm; With 532 nm nanosecond pulsed laser excitation. In deaerated toluene (c = 1.0 ×10-5

M, 20 °C).

Fig. S16 (a) Nanosecond time-resolved transient difference absorption spectra of H2TPTBP, (b) decay

trace at 510 nm; With 532 nm nanosecond pulsed laser excitation. In toluene (c = 1.0 ×10-5 M, 20 °C).

200 400 600 800 10000.00

0.04

0.08

0.12b

τT = 137 μs

Δ O

. D.

Time / μs

400 500 600 700-0.3

-0.2

-0.1

0.0

0.1 a

Δ O

. D.

Wavelength / nm

294 μs288 μs ...... ...... 6 μs 0 μs

400 500 600 700

-0.2

-0.1

0.0

0.1a

1500 ns1440ns ...... ...... 60 ns 0 ns

Δ O

. D.

Wavelength / nm

1500 3000 4500 60000.00

0.04

0.08

0.12b

τT = 236 ns

Δ O

. D.

Time / ns


S13

Fig. S17 (a) Delayed fluorescence observed in the TTA upconversion with ZnTPTBP as the triplet photosensitizer

and A-2 as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser, synchronized with FLS 920

spectrofluorometer) and the emission was monitored at 450 nm. Under the circumstances, compound ZnTPTBP is

selectively excited and the emission is due to the upconverted emission of the triplet acceptor A-2. (b) The decay

trace of the prompt fluorescence of A-2 determined in a different experiment (excited with picosecond 405 nm

laser; the decay of the emission was monitored at 450 nm). In deaerated toluene; c [Photosensitizer]= 2.0 × 10−6 M; c

[Triplet energy acceptor A-2]= 4.0 × 10−5 M; 20 °C.


and A-1 as the triplet energy acceptor. Excited at 654 nm (nanosecond pulsed OPO laser synchronized with FLS 920

spectrofluorometer) and the emission was monitored at 545 nm. Under the circumstances, ZnTPTBP was

selectively excited and the emission is due to the upconverted emission of the triplet acceptor A-1. (b) The decay

trace of the prompt fluorescence of A-1 determined in a different experiment (excited with 405 nm picosecond

pulsed laser; the decay of the emission was monitored at 545 nm). In deaerated toluene; c[Triplet

photosensitizers]= 2.0 × 10−6 M; c [Acceptor A-1] = 4.0 × 10−5 M; 20 °C.

0 500 1000 1500 20001

10

100

1000 aτDF = 159.7 μs

Cou

nts

Time / μs0 20 40 60 80 100

10

100

1000 bτPF = 4.3 ns

Cou

nts

Time / ns

0 500 1000 1500 2000

10

100

1000 aτDF = 184.4 μs

Cou

nts

Time / μs0 20 40 60 80 100

10

100

1000 bτPF = 5.8 ns

Cou

nts

Time / ns


S14


and PBI as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser synchronized with FLS 920

spectrofluorometer) and the emission was monitored at 539 nm. Under the circumstances, ZnTPTBP is selectively

excited and the emission is due to the upconverted emission of the triplet acceptor PBI. (b) The prompt

fluorescence decay of PBI determined in a different experiment (excited with 405 nm picosecond pulsed laser; the

decay of the emission was monitored at 539 nm). In deaerated toluene; c[Triplet photosensitizers]= 2.0 × 10−6 M; c

[Triplet energy acceptor PBI]= 4.0 × 10−5 M; 20 °C.

Fig. S20 Delayed fluorescence observed in the TTA upconversion with PdTPTBP as the triplet photosensitizer and

A-1 as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser synchronized with spectrofluorometer)

and the emission was monitored at 545nm. Under the circumstances, PdTPTBP is selectively excited and the

emission is due to the upconverted emission of triplet acceptor. In deaerated toluene; c[Sensitizers]=2.0 × 10−6M; c

[Acceptor] = 4.0 × 10−5M; 20 °C.

0 500 1000 1500 20001

10

100

1000a

τDF = 114.9 μs

Cou

nts

Time / μs0 20 40 60 80 100

10

100

1000 bτPF = 5.6 ns

Cou

nts

Time / ns

0 500 1000 1500 2000

10

100

1000τDF = 211.4 μs

Cou

nts

Time / μs


S15

Fig. S21 Delayed fluorescence observed in the TTA upconversion with PdTPTBP as the triplet photosensitizer and

A-2 as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser synchronized with FLS 920

spectrofluorometer) and the emission was monitored at 450 nm. Under the circumstances, Pd TPTBP is selectively

excited and the emission is due to the upconverted emission of triplet acceptor. In deaerated toluene;

c[Sensitizers]=2.0 × 10−6M; c [Acceptor] = 4.0 × 10−5M; 20 °C.

Fig. S22 Delayed fluorescence observed in the TTA upconversion with compound (a)Pd TPTBP and (b)H2TPTBP as

the triplet photosensitizer and PBI as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser

synchronized with spectrofluorometer) and monitored at 539 nm. Under the circumstances, compound is

selectively excited and the emission is due to the upconverted emission of triplet acceptor. In deaerated toluene;

c[Sensitizers]=2.0×10−6M; c [Acceptor]= 4.0 × 10−5 M; 20 °C.

0 500 1000 1500 2000

10

100

1000τDF = 165.5 μs

Cou

nts

Time / μs

0 500 1000 1500 20001

10

100

1000 a

τDF = 86.9 μs

Cou

nts

Time / μs0 500 1000 1500 2000

10

100

1000 bτDF = 118.2 μs

Cou

nts

Time / μs


S16

Fig. S23 Upconversion of H2TPTBP with A-1, A-2 and PBI as the triplet acceptor. Excited with 654 nm laser diode

(12 mW, 95.5 mW cm-2). In deaerated toluene. c [Sensitizer] = 2.0 × 10-6 M, c [Acceptor] = 4.0×10-5 M. 20 °C.

Fig. S24 Upconversions with triplet photosensitizer PdTPTBP. A-1 was used as triplet acceptor.

Emission of the sensitizers in the presence of triplet acceptor A-1. Excited with 635 nm laser (4.8

mW). c [sensitizer] = 2.0 × 10-6 M; c [A-1] = 4.0×10-5 M; in deaerated Toluene, 20 °C.

500 600 700 8000

5

10

15

20

25

*

(+ A-1/ A-2)+ PBI

H2 TPTBP

In

tesi

ty (a

.u.)

Wavelength / nm

N

N

O O

O O

PBIA-2

N B NF F

A-1

500 600 700 800 9000

100

200

300

400

(+ A-1)

*

Pd TPTBP

Inte

nsity

/ a.

u.

Wavelength / nm


S17

Fig. S25 The Stern-Volmer plot of ZnTPTBP, H2TPTBP and PdTPTBP with (a) A-1 and (b) PBI as the

triplet acceptor. c [Sensitizer] = 2.0 × 10-6 M. In deaerated toluene. 20 °C. Note the quenching was

determined with A-1 at low concentration.

0.0 4.0x10-6 8.0x10-60.0

0.4

0.8

1.2a

H2TPTBP

Zn TPTBP

Pd TPTBP

(τ0/τ

)-1

c[A-1] / M

0.0 5.0x10-6 1.0x10-50.0

2.0

4.0

6.0

H2 TPTBP

Pd TPTBP

Zn TPTBPb

(τ0/τ

)-1

c[PBI] / M


S18

Fig. S26 Time-resolved emission spectra (TRES) of the TTA upconversion with H2TPTBP as the triplet

photosensitizer and PBI as the triplet acceptor. (a) H2TPTBP alone, τF= 100.6 μs (λem = 700 nm), which

is the delayed fluorescence of H2TPTBP. (b) H2TPTBP/PBI upconversion mixture, τDF = 122.4 μs (λem=

540 nm). Time-resolved emission spectra and intensity decays were recorded using emission mode.

The samples were excited using nanosecond pulsed OPO laser (654 nm) c [Photosensitizer] = 2.0 ×

10-6 M. c [PBI] = 4.0 × 10-5 M. In deaerated toluene. 20 °C.

0200400600800

10001200140016001800

500550

600650

700750

800850

0100200300400500

PL In

tens

ity (a

.u.)

Wavele

ngth / nm

Time / μs

(b)

050

100150200250300350

600

650

700

750

800850

0100200300400500

PL In

tens

ity (a

.u.)

Wavele

ngth / nm

Time / μs

(a)


S19

Fig. S27 Time-resolved emission spectra (TRES) of the TTA UC with A-1 as triplet acceptor. (a)

PdTPTBP alone. τP = 223.7 μs (λem= 790 nm). (b) PdTPTBP/A-1, τDF = 202.5 μs (λem= 550 nm). Excited

using nanosecond pulsed OPO laser (654 nm). c [Photosensitizers] = 2.0 × 10-6 M. c [A-1] = 4.0 × 10-5

M in deaerated toluene; 20 °C.

0200400600800

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700720

740760780800820840

0100200300400500600

PL In

tens

ity (a

.u.)

Wav

eleng

th / n

Time / μs

(a)

0

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600

800

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Inte

nsity

(a.u

.)

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ngth

/ nm

Time / μs

(b)


Zinc(II) tetraphenyltetrabenzoporphyrin complex as triplet ...S1 Electronic Supplementary...

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