Supporting Information - Royal Society of Chemistry · Supporting Information ... (Bruker Daltonics GmbH) mass spectrometer, which was equipped with an automatic syringe pump for

1

Supporting Information

A multidonor-Photosensitizer-multiacceptor Triad for Long-Lived Directional Charge Separation

Tina Schlotthauer,a Robert Schroot,a Starla Glover,b Leif Hammarström,b Michael Jäger,a,c,* and Ulrich S. Schuberta,c,*

a Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller

University Jena, Humboldtstraße 10, 07743 Jena, Germany b Department of Chemistry - Ångström Laboratory, Uppsala University, Box 523,

SE75120 Uppsala, Sweden c Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller

University Jena, Philosophenweg 7a, 07743 Jena

Content

1. Instrumentation ............................................................................................................. 2 2. Syntheses ....................................................................................................................... 3 3. NMR spectroscopy ........................................................................................................ 6 4. Mass spectrometry ...................................................................................................... 12 5. Size-exclusion chromatography .................................................................................. 14 6. Steady state optical data .............................................................................................. 16 7. Spectroelectrochemical data ....................................................................................... 17 8. Time-resolved data ...................................................................................................... 18 8.1. Emission data ........................................................................................................... 18 8.2. Transient absorption data ......................................................................................... 21

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2017

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1. Instrumentation

NMR spectra were recorded on a 300 or 600 MHz NMR spectrometer (Bruker AVANCE or Fourier 300) in deuterated solvents at 300 K. Chemical shifts are reported in parts per million (ppm, δ scale) relative to the residual solvent signal.1

MALDI-TOF MS spectra were measured using an Ultraflex III TOF/TOF (Bruker Daltonics GmbH) equipped with a Nd:YAG laser and a collision cell. The spectra were recorded in the positive reflector or linear mode.

ESI-Q-TOF MS measurements were executed on a micrOTOF (Bruker Daltonics GmbH) mass spectrometer, which was equipped with an automatic syringe pump for sample injection. The pump was supplied from KD Scientific. It was operated in the positive ion mode. The standard electrospray ion (ESI) source was used to generate ions. Mixtures of dichloromethane and acetonitrile were used as solvent. The ESI-Q-TOF-MS instrument was calibrated in the m/z range 50 to 3,000 using an internal calibration standard (Tunemix solution), which was supplied from Agilent.

UV/Vis absorption spectra were measured on a Perkin-Elmer Lambda 45 UV/Vis spectrophotometer and emission as well as excitation spectra were recorded using a Jasco FP6500. Measurements were carried out using approx. 10-7 M solutions of aerated dichloromethane (spectroscopy grade) in 1 cm quartz cuvettes at 25 °C.

Flash column chromatography was carried out on a Biotage Isolera One System using Biotage SNAP Cartridges KP-Sil. The Biotage Initiator Sixty Microwave synthesizer was used for microwave reactions.

Preparative size exclusion chromatography was either performed by using Bio-Beads (S-X1, dichloromethane) or Toyopearl (HW-55F, CH2Cl2/MeOH 95/5).

Analytical size exclusion chromatography was performed on the following systems: SEC1. Shimadzu system (controller: SCL-10A VP, degasser: DGU-14A, pump: LC-10AD VP, auto sampler: SIL-10AD VP, oven: Techlab, UV detector: SPD-10AD VP, RI detector: RID-10A, eluent: chloroform/iso-propanol/triethylamine [94:2:4], flow rate: 1 mL/min, temperature: 40 °C, column: PSS SDV pre/lin S column). SEC2. Shimadzu system (controller: SCL-10A VP, degasser: DGU-14A, pump: LC-10AD VP, auto sampler: SIL-10AD VP, oven: CTO-10A VP, UV detector: SPD-10MA VP, RI detector: RID-10A, eluent: DMAc + 0.08% NH4PF6, flow rate: 1 mL/min, temperature: 40 °C, column: Phenomenex Phenogel guard/105 Å/103 Å)

Time-correlated single photon counting was performed on a Edinburgh Instrument (EPL405), equipped a Hamamatsu MCP-photomultiplier (R3809U-51) for detection of single photons as described previously.2 The laser’s pulse energy was (ca. 15 pJ, 77 ps pulses) and attenuated to a count rate of ca. 1% or less of the excitation frequency. Specific measurements were performed with 470 nm excitation with a repetition rate of 20 µs using a long pass filter (715 nm) or 3C1 Russian Filter which transmits light at λmax 540 with FWHM ca. 100 nm.3 The IRF has not been deconvoluted from the traces.

Time-resolved flash photolysis measurements were made with a frequency tripled Q-switched Nd:YAG laser (from Quantel, brilliantB) where 355 nm pulses with a 7 ns duration were directed through an OPO tuned to output of 500 or 532 nm at ca. 10-20 mJ/pulse. Analyzing light was supplied by a pulsed 150

3

W xenon lamp in a flash photolysis spectrometer (Applied Photophysics, LKS.80). Light that passed through the sample was sent through a monochrometer set to a bandwidth of 7 nm prior to reaching the 5 stage P928 photomultiplier tube (Hamamatsu). The signal was digitized using an Agilent Technologies Infiniium digital oscilloscope (600 MHz). Transient absorption traces were generated within the Applied Photophysics LKS software package where rates for each sample condition were determined from 24–64 laser shots. All emission measurements were performed in 1 × 1 cm quartz cuvettes in DCM.

Figure S1. Reaction vessel used for the polymerization.

2. Syntheses

All reagents were purchased from ABCR, Acros Organics, Alfa Aesar, Apollo Scientific, Sigma-Aldrich or TCI chemicals and were used without further purification unless otherwise noted. Dry pyridine and dry N-N-dimethylformamide (DMF) were commercially available. THF was distilled from sodium/benzophenone. All solvents were degassed before use. N-N-bis(4-butylphenyl)-(4-vinyl)aniline (1),4 N-(2-Ethyl-hexyl)-N’-(vinylphenyl)-naphthalene-1,4,5,8-dicarboxydiimide (2),5 [Ru(dqp-OH)(CH3CN)3][PF6]2,

6 4-bromophenyl-2,6-di(quinolin-8-yl)pyridine7, P,6 Dn‒P,4 and P‒Am5 were

prepared as previously described. Dqp-OH is 4-hydroxy-2,6-di(quinolin-8-yl)pyridine), PMDETA is N,N,N′,N′′,N′′-pentamethyldiethylenetriamine.

4-(4-(Triisopropylsilyl)ethinyl)phenyl-2,6-di(quinolin-8-yl)pyridine (dqp-ph-C≡C-TIPS). A flask was charged with 4-bromophenyl-2,6-di(quinolin-8-yl)pyridine (0.700 g, 1.433 mmol), Pd(PPh3)4 (0.099 g, 0.086 mmol) and copper(I) iodide (0.016 g, 0.086 mmol), sealed and placed under a nitrogen atmosphere. Then dry THF (50 mL), dry triethylamine (25 mL) and triisopropylsilylacetylene (0.6 mL, 2.674 mmol) were added via a syringe and the mixture was heated to 60 °C for 16 h until the TLC (CH2Cl2/MeOH 99/1, silica) showed full conversion. The reaction mixture was allowed to cool to room temperature and was filtered over Celite. The solvents were removed under reduced pressure and the residual crude product was purified by flash column chromatography (silica, eluent: CH2Cl2/EtOAc 90/10 followed by CH2Cl2/MeOH 99/1). The combined product-containing fractions were dried in vacuo to yield the product as off-white solid. (0.695 g, 85%). 1H NMR (250 MHz, CDCl3): δ 9.08–8.93 (m, 2H), 8.37–8.19 (m, 6H), 7.90 (d, J = 8.1 Hz, 2H), 7.78 (d, J = 7.7 Hz, 2H), 7.68 (t, J = 7.7 Hz, 2H), 7.60 (d, J = 7.7 Hz, 2H), 7.46 (dd, J = 8.1, 4.0 Hz, 2H), 1.15 (s, 21H). 13C NMR (63 MHz, CDCl3): δ 157.5, 150.5, 146.4, 146.2, 139.5, 139.4, 136.5, 132.7, 131.7, 128.8, 128.7, 127.5, 126.8, 123.9, 123.8, 121.1, 107.0, 92.1, 18.8, 11.5. MS (MALDI-ToF, DCTB) m/z: 590.39 ([C40H39N3Si+H]+). HR-ESI ([C40H39N3Si+H]+) m/z: calc: 590.2986, found: 590.2964, Error: 3.7 ppm.

4

Poly(triaryl amine) (pTARA). A glass tube equipped with a septum and an external overhead flushing with nitrogen was used for the polymerization (Figure S1). The reaction vessel was charged with 1 (0.940 g, 2.451 mmol), N-(tert-butyl)-O-(1-(4-(chloromethyl)phenyl)ethyl)-N-(2-methyl-1-phenylpropyl)hydroxylamine (CMSt-TIPNO) (0.046 g, 0.123 mmol) and anisole (2.4 mL).The mixture was purged with nitrogen for 20 min and placed in a pre-heated oil bath (120 °C). After 23 h the reaction mixture was diluted with CH2Cl2 and precipitated in cold MeOH. Subsequently, unreacted monomer was removed by preparative SEC (Bio-Beads S-X1, CH2Cl2). The polymer was obtained as yellow solid after precipitation in MeOH. Yield: 0.465 g. SEC (CHCl3/2-propanol/NEt3 94/2/4, PS calibration): Mn = 4,600 g/mol, Ð = 1.06. 1H NMR (300 MHz, CDCl3): δ 7.56 – 7.06 (br), 7.06 – 6.13 (br), 4.60 – 4.21 (br), 2.72 – 2.65 (br), 2.65 – 1.78 (br), 1.78 – 1.42 (br). 1.42 – 1.18 (br), 1.18 – 0.74 (br), 0.74 – 0.11 (br).

Poly(naphthalene diimide) (pNDI, Cl-decorated). A glass tube equipped with a septum and an external overhead flushing with nitrogen was used for the polymerization (Figure S1). The reaction vessel was charged with 2 (0.500 g, 1.040 mmol), N-(tert-butyl)-O-(1-(4-(chloromethyl)phenyl)ethyl)-N-(2-methyl-1-phenylpropyl)hydroxylamine (CMSt-TIPNO) (0.019 g, 0.052 mmol) and anisole (4.0 mL).The mixture was purged with nitrogen for 20 min and placed in a pre-heated oil bath (120 °C). After 17 h the reaction mixture was diluted with CH2Cl2 and precipitated in cold MeOH. Subsequently, unreacted monomer was removed by preparative SEC (Bio-Beads S-X1, CH2Cl2). The polymer was obtained as yellow solid after precipitation in MeOH. Yield: 0.400 g. SEC (CHCl3/2-propanol/NEt3 94/2/4, PS calibration): Mn = 6,400 g/mol, Ð = 1.11. 1H NMR (300 MHz, CDCl3): δ 9.04 – 7.98 (br), 7.78 – 6.67 (br), 4.72 – 4.42 (br), 4.34 – 3.60 (br), 2.91 – 1.72 (br), 1.52 – 1.04 (br). 1.04 – 0.45 (br).

Poly(naphthalene diimide) (pNDI, azide-decorated). Safety advice: Sodium azide is very toxic, personal protection precautions should be taken. Heavy metal azides are explosive. Do not use metal spatula. A glass vial was charged with pNDI (Cl-decorated) (0.150 g, 0.024 mmol, 1 eq.) and sodium azide (0.005 g, 0.071 mmol, 3 eq.), capped and placed under a nitrogen atmosphere. Dry DMF (4.5 mL) was added and the reaction mixture was immersed in an oil bath at 60 °C at which the polymer dissolved. After 48 h CH2Cl2 and water were added to the formed suspension and the layers were separated. The aqueous layer was extracted two times with CH2Cl2. The combined organic layers were three times washed with brine and dried over Na2SO4. After removal of the solvent under reduced pressure, a yellow solid was obtained. Yield: 0.135 g. SEC (CHCl3/2-propanol/NEt3 94/2/4, PS calibration): Mn = 6,300 g/mol, Ð = 1.08. 1H NMR (300 MHz, CDCl3): δ 9.04 – 7.98 (br), 7.78 – 6.66 (br), 4.56 – 4.22 (br), 4.23 – 3.60 (br), 2.83 – 1.65 (br), 1.51 – 1.05 (br), 1.05 – 0.45 (br). Note: The quantitative substitution was verified by a shift of the methylene proton resonance of pNDI (azide-decorated). (from 4.6 ppm to 4.3 ppm).

[Ru(dqp-OH)(dqp-ph-C≡C-TIPS)][PF6]2. A flask was charged with [Ru(dqp-OH)(CH3CN)3][PF6]2 (0.450 g, 0.521 mmol), dqp-ph-C≡C-TIPS (0.307 g, 0.521 mmol) and dry DMF (10 mL) under nitrogen. Subsequently the reaction mixture was heated to 140 °C for 48 h. After cooling to room temperature the solution was precipitated in an aqueous NH4PF6 solution, filtered and re-dissolved in CH3CN. The crude product was purified by column chromatography on silica using a mixture of CH3CN/H2O/KNO3(aq) (40/4/1) as eluent. Afterwards on anion exchange was performed by precipitation in an aqueous NH4PF6 solution. Finally, diffusion controlled crystallization (diethyl ether into acetonitrile solution) gave the desired complex as red solid (0.350 g, 51%). 1H NMR (600 MHz, CD3CN): δ 9.15 (br, OH), 8.13 (m, 4H), 8.06 (m, 6H), 7.93 (d, J = 8.5 Hz, 2H), 7.86 (dd, J = 1.1 Hz, 7.5 Hz, 2H), 7.71 (dd, J = 1.1 Hz, 7.3 Hz, 2H), 7.67 (m, 6H), 7.45 (m, 4H), 7.37 (s, 2H), 7.07 (m, 4H), 1.16 (m, 21H). 13C NMR (150 MHz, CD3CN): δ 166.2, 159.6, 159.5, 158.5, 158.2, 149.1, 147.6 (2×), 138.4, 138.3, 137.1, 134.3, 133.7, 133.6, 132.9, 132.6, 131.5 (2×), 128.6, 127.7, 127.6, 127.5, 126.1, 125.9, 122.9, 116.7, 107.2, 94.2,

5

18.9, 12.0. HR-ESI-ToF-MS: [C63H54N6ORuSi]2+ m/z: calculated: 520.1580, found: 520.1599, error: 1.9 ppm.

[Ru(dqp-O-pTARA)(dqp-ph-C≡C-TIPS)][PF6]2. A vial was charged with pTARA (0.400 g, 0.087 mmol) and anisole (1.5 mL). Then [Ru(dqp-OH)(dqp-ph-C≡C-TIPS)][PF6]2 (0.231 g, 0.174 mmol), KI (0.029 g, 0.174 mmol), K2CO3 (0.024 g, 0.174 mmol) and DMF (1.5 mL) were added. Subsequently, the vial was capped and immersed in a preheated oil bath at 60 °C. The reaction progress was monitored by UV/vis SEC and TLC (aluminium oxide, CH2Cl2/MeOH 95/5). After 89 h no further conversion was detected and the reaction mixture was cooled to room temperature. An aqueous solution of NH4PF6 was added and the suspension was extracted with CH2Cl2 (3 ×). The organic extracts were dried over Na2SO4 and concentrated under reduced pressure. The desired dyad was isolated by preparative SEC (Toyopearl HW-55F, CH2Cl2/MeOH 95/5) as red solid (0.250 g, 48%). 1H NMR (600 MHz, CD2Cl2): δ 8.17 (br, Ru), 8.10 (br, Ru), 7.96 (br, Ru), 7.73 (br, Ru), 7.60 (br, Ru), 7.53 (br, Ru), 7.39 (br, Ru), 7.26 (br, Ru), 7.05 – 5.81 (br, p115), 5.46 (br, linker), 5.24 (br, linker), 2.64 – 2.34 (br, (br, p115), 2.34 – 1.85 (br, p115), 1.85 – 1.43 (br, p115). 1.43 – 1.22 (br, p115), 1.22 – 1.15 (br, TIPS), 1.00 – 0.72 (br, p115).

[Ru(dqp-O-pTARA)(dqp-ph-C≡C-H)][PF6]2. A vial was charged with [Ru(dqp-O-pTARA)(dqp-ph-C≡C-TIPS)][PF6]2 (0.230 g, 0.038 mmol) under nitrogen. Then dry THF (5.0 mL) was added and the resulting solution was cooled with an ice bath. Subsequently, a solution of (n-Bu4)NF (0.040 g, 0.143 mmol) in THF (0.265 mL) was added and the mixture was stirred for 0.5 h at 0 °C. Afterwards, water was added and the solution was extracted with CH2Cl2. The organic extracts were dried over Na2SO4 and concentrated under reduced pressure. The red solid was washed with CH3CN and was dried (0.230 g, 100%). 1H NMR (300 MHz, CD2Cl2): δ 8.04 (br, Ru), 7.99 (br, Ru), 7.79 (br, Ru), 7.65 (br, Ru), 7.51 (br, Ru), 7.33 (br, Ru), 7.14 (br, Ru), 7.04 – 6.30 (br, p115), 5.14 (br, linker), 2.63 – 2.28 (br, p115), 2.25 – 1.62 (br, p115), 1.62 – 1.39 (br, p115). 1.39 – 1.18 (br, p115), 0.97 – 0.74 (br, p115).

[Ru(dqp-O-pTARA)(dqp-ph-trz-pNDI)][PF6]2 (Dn‒P‒Am). A vial was charged with [Ru(dqp-O-pTARA)(dqp-ph-C≡C-H)][PF6]2 (0.014 g, 0.003 mmol, 1 eq.) and pNDI (azide-decorated) (0.030 g, 0.005 mmol, 2 eq.) under nitrogen. Then dry DMF (1.0 mL), solution of CuBr (0.001 g, 0.010 mmol, 4 eq.) in DMF (0.2 mL) and PMDETA (0.24 M in DMF, 0.04 mL, 4 eq.) were added. The mixture was heated to 80 °C for 96 h. The mixture was precipitated in aqueous NH4PF6 and the red solid was extracted with CH2Cl2. After drying over Na2SO4, the desired triad Dn‒P‒Am was purified by preparative size-exclusion chromatography (Toyopearl HW-55F, CH2Cl2/MeOH 95/5, two runs) and was isolated as light red solid (0.017 g, 58%). 1H NMR (300 MHz, CD2Cl2): δ 8.84 − 8.17 (br, p217), 8.08 (br, Ru), 7.91 (br, Ru), 7.68 (br, Ru), 7.64 − 7.04 (br, Ru + p217), 7.04 – 6.29 (br, p115), 5.57 (br, linker), 5.20 (br, linker), 4.32 − 3.58 (br, p217), 2.96 – 2.29 (br, p115), 2.29 – 1.59 (br, p115 + p217), 1.59 – 1.44 (br, p115). 1.39 – 1.04 (br, p115 + p217), 1.04 – 0.46 (br, p115 + p217).

6

3. NMR spectroscopy

Figure S2. 1H NMR spectrum (300 MHz, CDCl3) of pTARA.

Figure S3. 1H NMR spectrum (300 MHz, CDCl3) of pNDI (Cl-decorated). Note the chloromethyl group at 4.57 ppm.

7

Figure S4. 1H NMR spectrum (300 MHz, CDCl3) of pNDI (azide-decorated).

Figure S5. 1H NMR spectrum (600 MHz, CD3CN) of [Ru(dqp-OH)(dqp-ph-C≡C-TIPS)][PF6]2.

8

Figure S6. 13C NMR spectrum (150 MHz, CD3CN) of [Ru(dqp-OH)(dqp-ph-C≡C-TIPS)][PF6]2.

Figure S7. H,H COSY spectrum of [Ru(dqp-OH)(dqp-ph-C≡C-TIPS)][PF6]2.

9

Figure S8. HSQC spectrum of [Ru(dqp-OH)(dqp-ph-C≡C-TIPS)][PF6]2.

Figure S9. HMBC spectrum of [Ru(dqp-OH)(dqp-ph-C≡C-TIPS)][PF6]2.

10

Figure S10. 1H NMR spectrum (300 MHz, CD2Cl2) of [Ru(dqp-O-pTARA)(dqp-ph-C≡C-TIPS)][PF6]2. Note the downfield shift of the methylene group upon linkage (from 4.57 in Figure S3) to 5.5 ppm.

Figure S11. H,H COSY spectrum of [Ru(dqp-O-pTARA)(dqp-ph-C≡C-TIPS)][PF6]2.

11

Figure S12. 1H NMR spectrum (300 MHz, CD2Cl2) of [Ru(dqp-O-pTARA)(dqp-ph-C≡CH)][PF6]2.

Figure S13. 1H NMR spectrum (300 MHz, CD2Cl2) of [Ru(dqp-O-pTARA)(dqp-ph-trz-pNDI)][PF6]2 (Dn‒P‒Am).

12

4. Mass spectrometry

400 600 800 1000 1200 1400

[M+H-2PF6]+

m/z

[M-2PF6]2+

516 518 520 522 524

m/z

experimental

calculated

Figure S14. ESI TOF MS data of [Ru(dqp-OH)(dqp-ph-C≡C-TIPS)][PF6]2 and (right) comparison of measured and calculated isotope pattern.

2000 4000 6000 8000 10000 12000 14000

m/z

480 amu

Figure S15. MALDI TOF mass spectrum of pNDI (Cl-decorated) (matrix: HABA + NaTFA) with proposed structure of the main series.

N

N

OO

OOEtHex

CH•

N

N

OO

OOEtHex

Cl Na+

n-1

13

7375 7400 7425 7450

m/z

(C30H28N2O4)15C9H10Cl + K+

(C30H28N2O4)15C9H10Cl + Na+

pNDI (Cl-decorated)

Figure S16. Theoretical (top) isotopic patterns to fit the experimental (bottom) data of the signal corresponding to a DP = 15 (matrix: HABA + NaTFA).

2000 4000 6000 8000 10000 12000 14000

m/z

480 amu

Figure S17. MALDI TOF mass spectrum of pNDI (azide-decorated) (matrix: HABA + NaTFA) with proposed structure of the main series.

7375 7400 7425 7450

m/z

(C30H28N2O4)15C9H10NO + Na+

(C30H28N2O4)15C9H10N3 + K+

(C30H28N2O4)15C9H10N3 + Na+

(C30H28N2O4)15C9H10N3 + H+

pNDI (azide-decorated)

Figure S18. Theoretical (top) isotopic patterns to fit the experimental (bottom) data of the signal corresponding to a DP = 15 (matrix: HABA + NaTFA).

N

N

OO

OOEtHex

CH•

N

N

OO

OOEtHex

NO

n-1

Na+

14

5. Size-exclusion chromatography

8.0 8.5 9.0 9.5 10.0 10.5

0.0

0.2

0.4

0.6

0.8

1.0

norm

aliz

ed U

V-in

tens

ity

volume [mL]

pNDI (Cl-decorated) pNDI (azide-decorated)

Figure S19. SEC elugrams of pNDI (Cl-decorated and azide-decorated) showing the absence of degradation during the functionalization (UV: 340 nm detection wavelength, CHCl3, iso-propanol, triethylamine 94/2/4).

Figure S20. 3D SEC data (wavelength vs elution time, DMAc + 0.08% NH4PF6) of [Ru(dqp-O-pTARA)(dqp-ph-C≡C-TIPS)][PF6]2 (Dn‒P) with projections: (top) UV trace at 20.03 mL; (right) chromatogram at 500 nm in a.u..

15

Figure S21. 3D SEC data (wavelength vs elution time, DMAc + 0.08% NH4PF6) of [Ru(dqp-O-pTARA)(dqp-ph-trz-pNDI)][PF6]2 (Dn‒P‒Am) with projections: (top) UV trace at 20.03 mL; (right) chromatogram at 500 nm in a.u..

16

6. Steady state optical data

300 400 500 600 700 800 9000.0

0.5

1.0

1.5

2.0

2.5polymer-basedemission

triad

dyad

pNDI pTARA

scal

ed a

bsor

ptio

n [a

. u.]

wavelength [nm]

-96%

3MLCT emission

Ru

0

10

20

30

emis

sion

inte

nsity

Figure S22. Enlarged version: Absorption spectra (left axis) of the triad (black curve, circles), including its precursor dyad (grey curve, rectangles) and the polymeric building blocks pTARA (blue-shaded area) and pNDI (green-shaded area). Note the absorption band of the single Ru photosensitizer unit (400‒600 nm). Steady-state emission spectra (right axis) of the precursor dyad (grey dashed line, rectangles) and the triad (black dashed line, circles). Note polymer-based emission (<650 nm) and the 3MLCT emission (around 700 nm), the latter one quenched by 96% comparing donor dyad (Dn‒P) and full triad (Dn‒P‒Am) (subtracting residual polymer-based emission). All measurements were performed in aerated DCM solution, asterisk (*) denotes Raman artefacts.

* *

17

7. Spectroelectrochemical data

01x104

2x104

3x104

300 400 500 600 700 8000

1x104

2x104

3x1040

1x104

2x104

pTARA

RuIII (at +0.9 V)

wavelength [nm]

RuII

pTARA+ (at +0.5 V)ab

sorp

tion

coef

ficie

nts

[M-1

cm

-1]

pNDIpNDI- (at -2.1 V)

Figure S23. Spectro-electrochemical data (in 0.1 M nBu4NPF6 in CH2Cl2, potentials vs. Fc+/0) of the pTARA block (top), the pNDI block (middle), and the reference complex [Ru(dqp)2]2+ (bottom). Spectroelectrochemical data taken from refs. 5, 8

18

8. Time-resolved data

8.1. Emission data

0 2,000 4,000 6,000 8,000

0.00

0.01

0.02

0.03

0.04

0.05

inte

nsity

[a.u

.]

time [ns]

P monoexponential fit residuals

model exponential decay

equation y = y0 + A1*exp(-(x-x0)/t1)

chi2 reduced4.60616E-8

cor. R2 0.99916value standard deviation

Ru y0 4.18669E-5 8.85789E-6

--

x0 3.75669E-8 --A1 0.03939 --t1 7.62512E-7 1.53689E-9

0 1,000 2,000 3,000 4,000-0.01

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

inte

nsity

[a.u

.]

time [ns]

DnP (emission at 690 nm) exponential fit residuals

model mono-exponential


chi2 reduced9.04425E-

9


Ru-pTARA y0 -4.37205E- 4.93541E-6

--x0 1.62395E-8 0.03025A1 0.00597 273.63192t1 6.60271E-7 3.42903E-9

-50 0 50 100 150 200-0.01

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07 DnP (emission at 690 nm) monoexponential fit residuals excitation pulse

inte

nsity

[a.u

.]

time [ns]-50 0 50 100 150 200

0.00

0.05

0.10

0.15

0.20

0.25

inte

nsity

[a.u

.]

time [ns]

excitation pulse PAm (emission at 690 nm) monoexponential fit residuals

model exponential



cor. R2 0.92516-- error standard deviation

Ru-pNDI y0 0.00108 3.79615E-5

--x0 1.17694E-8 --A1 0.02417 --t1 8.12105E-9 1.6719E-10

Figure S24. Emission data and respective fits for the reference systems: (a) Photosensitizer (P), (b) donor dyad (Dn‒P) with zoom of the pulse region (c), and (d) acceptor dyad (P‒Am) including pulse (green). Excitation pulse width (approximately 10 ns) determined from Raman scatter of a pure DCM sample.

(a) b)

(c) d)

19

Figure S25. Transmission properties of band pass filter (3C1) used in TCSPC measurements (λmax = 540 nm with FWHM ca. 100 nm. Note that blocked transmission above 650 nm, which is typical for the 3MLCT emission.

100 200 300 4001E-6

1E-5

1E-4

1E-3

0.01

0.1

1

norm

aliz

ed c

ount

s

time [ns]

DnPAm with long pass filter (715nm)

DnPAm with band pass filter 3C1 (450-650 nm)

IRF

50 60 70 80 90

1

10

100

1000

10000

coun

ts

time [ns]

DnPAm with long pass filter (715nm)

DnPAm with band pass filter 3C1 (450-650 nm)

IRF

Figure S26. Normalized time-correlated single photon counting data of Dn‒P‒Am (a) and expansion of pulse region (b). Instrument response function (IRF, blue, ca 1.3 ns), with long pass filter (>715 nm, black) and with band pass filter (3C1, 450-650 nm, red). See Figure S25 for transmission characteristics of 3C1 filter.

(a) b)

20

60 65 70 75 80 85 90 95 100

0

1000

coun

ts

time [ns]

with filter 3C1 (450-650nm) monoexponential fit residuals

Modell ExpDecay1

Gleichungy = y0 + A1*exp(-(x-x0)/t1)

Chi-Quadr Reduziert

58.85586

Kor. R-Quadra 0.98299Wert Standardfehler

Triad3C1filter

y0 12.41906 0.53049x0 6.23771E-8 6.37825E-4A1 340.80067 7.43112E7t1 2.92515E-9 4.4939E-11

60 65 70 75 80 85 90 95 100

0

1000

coun

ts

time [ns]

with filter 3C1 (450-650nm) biexponential fit residuals

Modell ExpDecay2

Gleichungy = y0 + A1*exp(-(x-x0)/t1) + A2*exp(-(x-x0)/t2)

Chi-Quadr Reduziert

34.9299


Triad3C1filter

y0 10.06542 0.50033x0 6.23049E-8 --A1 190.29284 --t1 9.84013E-10 1.11932E-10A2 229.19786 --t2 4.08588E-9 1.78191E-10

60 65 70 75 80 85 90 95 100

0

1000

coun

ts

time [ns]

with filter 3C1 (450-650nm) triexponential fit residuals

Modell ExpDecay3

Gleichungy = y0 + A1*exp(-(x-x0)/t1) + A2*exp(-(x-x0)/t2) + A3*exp(-(x-x0)/t3)

Chi-Quadr Reduziert

34.46462

Kor. R-Quadrat 0.99004Wert Standardfehler

Triad3C1filter

y0 9.12519 1.01193x0 6.26229E-8 --A1 78.66808 --t1 6.09664E-10 2.25463E-10A2 195.53596 --t2 2.57075E-9 1.00859E-9A3 80.09459 --t3 6.07951E-9 2.87437E-9

100 200 300 400

0

500

1000

1500

2000

coun

tstime [ns]

with long pass (>715 nm) monoexponential fit residuals

model biexponential

equationy = y0 + A1*exp(-(x-x0)/t1)

chi2 reduced725.27634


--y0 50.21275 0.56885x0 5.10078E-8 0.00174

long pass (>715 nm) A1 819.65706 4.95944E7-- t1 2.87371E-8 2.86216E-10

100 200 300 400

0

500

1000

1500

2000

coun

ts

time [ns]

with long pass (>715 nm) biexponential fit residuals

model biexponential

equationy = y0 + A1*exp(-(x-x0)/t1) + A2*exp(-(x-x0)/t2)



--y0 41.10611 0.28152x0 5.95743E-8 3.43621E-4

long pass (>715 nm) A1 1307.28311 1.29478E8

--t1 3.46938E-9 4.86726E-11A2 376.24541 2.63298E6t2 4.91025E-8 3.47868E-10

100 200 300 400

0

500

1000

1500

2000

coun

ts

time [ns]

with long pass (>715 nm) triexponential fit residuals

model biexponential

equationy = y0 + A1*exp(-(x-x0)/t1) + A2*exp(-(x-x0)/t2) + A3*exp(-(x-x0)/t3)



--y0 37.75039 0.35139x0 5.75455E-8 1.39675E-4

long pass (>715 nm) A1 6332.11314 4.62504E8

--t1 1.91228E-9 6.06554E-11A2 371.45362 4.0433E6t2 1.28318E-8 6.3396E-10A3 284.47992 631422.3513t3 6.29287E-8 1.11184E-9

100 200 300 400

0

500

1000

1500

2000

coun

ts

time [ns]

with long pass (>715 nm) tetraexponential fit residuals

model biexponential

equationy = y0 + A1*exp(-(x-x0)/t1) + A2*exp(-(x-x0)/t2) + A3*exp(-(x-x0)/t3)+ A4*exp(-(x-x0)/t4)



--y0 35.20564 0.75961x0 6.03797E-8 2.17512E-4

long pass (>715 n A1 3443.65023 1.07448E9

--t1 8.39029E-10 9.12518E-11A2 618.53185 3.39009E7t2 4.11768E-9 2.7989E-10A3 263.50061 2.03844E6t3 2.82676E-8 2.47466E-9A4 158.31993 405911.48932t4 8.49885E-8 6.82801E-9

Figure S27. TCSPC data and fits of Dn‒P‒Am using the band pass filter 3C1 (450‒650 nm, a-c), and the long pass filter (>715 nm, d-g) applying multiexponential fit curves: (a,d) Monoexponential, (b, e) biexponential, (c,f) triexponential and (g) tetraexponential decay.

a) b)

c) d)

e) f)

g) h)

21

0 100 200 300 400 500 600 700 800

1

2

3

4

5

6

7 k/k0

Linear Fit k/k0

k/k0

volume of NDI-solution [mL]

Equation y = a + b*xWeight No Weighting

Residual Sum of Squares 0.181Pearson's r 0.99667Adj. R-Square 0.9924

Value Standard ErrorIntercept 1.1064 0.09895Slope 0.00828 2.56009E-4

0 100 200 300 400 500 600 700 8000

1

2

3

4

5

6

7

8

9 emission area linear fit

I 0/I

volume of NDI-solution [mL]

Equation y = a + b*xWeight No Weighting

Reduced Chi-Sqr 0.03483R-Square 0.99447Pearson's r 0.99723

Value ErrorIntercept 1.01761 0.11484Slope 0.01054 2.97126E-4

Figure S28. Stern-Vollmer analysis for initial electron transfer between Ru unit and NDI units using the Dn-Ru dyad: Bimolecular quenching confirms dynamic quenching mechanism for non-linked systems.

Table S1. Tabulated fit parameters for TCSPC data of Dn‒P‒Am.

450-650 nm (3C1) >715 nm (long pass) monoexponential biexponential triexponential monoexponential biexponential triexponential tetraexponential Component1 2.92 ± 0.01 ns

(100%) 0.98 ± 0.11 ns (45%)

0.61 ± 0.23 ns (22%)

28.73 ± 0.28 ns (100%)

3.47 ± 0.05 ns (78%)

1.91 ± 0.06 ns (91%)

0.83 ± 0.09 ns (77%)

Component2 - 4.08 ± 0.18 ns (55%)

2.57 ± 1.01 ns (55%)

- 49.1 ± 0.34 ns (22%)

12.8 ± 0.64 ns (5%)

4.11 ± 0.28 ns (14%)

Component3 - - 6.08 ± 2.86 ns (23%)

- - 62.9 ± 1.11 ns (4%)

28.3 ± 2.5 ns (6%)

Component 4 85.0 ± 6.8 ns (4%)

χ2-reduced 58.856 34.930 34.465 725.28 116.79 94.823 90.813 Correlated R2 0.9830 0.9899 0.9900 0.9289 0.9886 0.9907 0.9911

8.2. Transient absorption data

400 450 500 550 600 650 700

-0.3

-0.2

-0.1

0.0

0.1

0.2

0.3

0.4

abso

rban

ce c

hang

es [a

.u.]

wavelength [nm]

20 ns 50 ns 100 ns 200 ns 500 ns 1,000 ns 2,000 ns 5,000 ns

400 450 500 550 600 650 700

-0.3

-0.2

-0.1

0.0

0.1

0.2

0.3

0.4

abso

rban

ce c

hang

es [a

.u.]

wavelength [nm]

-10.7 ns -0.7 ns 9.3 ns 19.3 ns 29.3 ns 39.3 ns

(a) b)

* *

22

0 2,000 4,000 6,000 8,000

-0.20

-0.15

-0.10

-0.05

0.00ab

sorb

ance

cha

nges

[a.u

.]

time [ns]

P (TA at 470 nm) monoexponential fit residuals

model exponential decay



cor R2 0.99953value standard deviation

Ru y0 -0.00102 3.15475E-5

--

x0 6.17138E-8 --A1 -0.19303 --t1 7.26055E-7 1.07949E-9

Figure S29. Transient absorption data of P: (a) Spectral recovery at selected times with zoom of pulse region (b). Note the isosbestic points around 435 and 575 nm. Asterisk denotes excitation pulse artefacts due to Rayleigh scatter. (c) Decay profile with fit at 470 nm.

c)

23

400 450 500 550 600 650 700

-0.4

-0.2

0.0

0.2

0.4

0.6ab

sorb

ance

cha

nges

[a. u

.]

wavelength [nm]


400 450 500 550 600 650 700

-0.8

-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6

abso

rban

ce c

hang

es [a

. u.]

wavelength [nm]

-1.3 ns 3.6 ns 8.6 ns 13.6 ns 18.6 ns 23.6 ns 28.6 ns 33.6 ns

0 1,000 2,000 3,000 4,000

-0.30

-0.25

-0.20

-0.15

-0.10

-0.05

0.00

0.05

abso

rban

e ch

ange

s [a

.u.]

time [ns]

DnP (TA at 470 nm) monoexponential fit residuals

model exponential

equationy = y0 + A1*exp(-(x-x0)/t1)

chi2 reduced1.76005E

-6


Ru-pTARA y0 0.00163 6.10638E-5

--x0 2.25799E-8 0.00601A1 -0.28659 3281.73409t1 5.24525E-7 8.18203E-10

0 1,000 2,000 3,000 4,000

-0.30

-0.25

-0.20

-0.15

-0.10

-0.05

0.00

0.05

abso

rban

ce c

hang

es [a

.u.]

time [ns]

DnP (TA at 470 nm) biexponential fit residuals

model biexponential


chi2 reduced8.92052E

-7


Ru-pTARA y0 0.00216 5.24017E-5

--

x0 7.38119E-8 0.00425A1 -0.01968 518.46928t1 1.6135E-7 1.07132E-8A2 -0.24416 1872.88069t2 5.54211E-7 2.28074E-9

400 450 500 550 600 650 700

-1.0

-0.5

0.0

0.5

1.0

norm

aliz

ed in

tens

ity [a

rb.u

.]

wavelength [nm]

Component 1 (6.3 ns) Component 2 (520 ns)

Figure S30. Transient absorption data of Dn‒P: (a) Spectral recovery at selected times with zoom of pulse region (b). Note the preserved isosbestic point around 435 nm but clear deviation at 575 nm with respect to Ru (Figure S29), as well as weaker TA signals between 575 and 650 nm assigned to additional polymer-based emission (see text). Asterisk denotes excitation pulse artefacts including Rayleigh scatter. (c) Decay profile with fit at 470 nm including biexponential decay (d). Global fit (>= 18.6 ns) with biexponential kinetics with corresponding amplitudes (scaled for comparison). Component 1 (black curve) shows similar spectral signatures as polymer-based emission from steady state data with comparable lifetimes (6.3 ns) as observed in TCSPC with band pass filter (Figure S27), while component 2 (red curve) resembles P in terms for its spectrum and lifetime (520 ns, Figure S29).

(a) b)

*

c) d)

e)

24

400 450 500 550 600 650 700

-0.15

-0.10

-0.05

0.00

0.05

0.10ab

sorp

tion

chna

ges

[a.u

.]

wavelength [nm]

20 ns 50 ns 100 ns 200 ns 500 ns 1000 ns

400 450 500 550 600 650 700

-0.3

-0.2

-0.1

0.0

0.1

0.2

abso

rban

ce c

hang

es [a

.u.]

wavelength [nm]

-4.7 ns -2.7 ns -0.7 ns 1.3 ns 3.3 ns 5.3 ns 7.3 ns 9.3 ns 11.3 ns 13.3 ns 15.3 ns 17.3 ns 19.3 ns 21.3 ns

0 500 1,000 1,500 2,000-0.05

-0.04

-0.03

-0.02

-0.01

0.00

abso

rban

ce c

hang

es [a

.u.]

time [ns]

Ru-pNDI (TA at 470 nm) biexponential fit residuals

model biexponential

equation y = y0 + A1*exp(-(x-x0)/t1) + A2*exp(-(x-x0)/t

chi2 reduced2.66349E-

7

cor R2 0.96058value standard deviation

Ru-pNDI y0 -4.53238E-4 2.53387E-5

--

x0 1.7537E-8 0.00473A1 -0.01928 4262.79738t1 2.13926E-8 5.93031E-10A2 -0.00425 93.26028t2 2.15691E-7 1.27471E-8

0 50 100 150 200 250 300-0.035

-0.030

-0.025

-0.020

-0.015

-0.010

-0.005

0.000

0.005

abso

rban

ce c

hang

es [a

.u.]

time [ns]

PAm (TA at 470 nm) biexponential fit residuals

Figure S31. Transient absorption data of P‒Am: (a) Spectral recovery at selected times with zoom of pulse region (b). Note the preserved isosbestic point around 435 nm but clear deviation at 575 nm with respect to Ru (Figure S29), as well as the more negative TA signals between 575 and 650 nm assigned to additional polymer-based emission (see text). Note the very weak TA features of pNDI‒ (475 nm) developing and decaying with excitation time window (maximal after 5.3 ns). After 21.3 ns, the typical 3MLCT without polymer-emission is observed. Asterisk denotes excitation pulse artefacts including Rayleigh scatter. (c) Decay profile with fit at 470 nm and zoom to pulse region (d), corroborating the charge separation and rapid charge recombination.

*

a) b)

c)

*

d)

25

0 2,000 4,000 6,000 8,000

0.000

0.005

0.010

0.015

0.020

0.025ab

sorb

ance

cha

nges

[a.u

.]

time [ns]

DnPAm at 420 nm triexponential fit residuals

Modell ExpDec3

Gleichungy = A1*exp(-x/t1) + A2*exp(-x/t2) + A3*exp(-x/t3) + y0

Chi-Quadr Reduziert

4.05403E-8


B

y0 5.03365E-6 2.50269E-4A1 0.01098 0.0017t1 2.87007E-7 2.85998E-8A2 0.01119 0.00131t2 8.10268E-7 1.10365E-7A3 0.00403 3.98556E-4t3 4.78487E-6 1.18898E-6

450 500 550 600 650 700 750-0.06

-0.04

-0.02

0.00

0.02

0.04

0.06

abso

rban

ce c

hang

es [a

.u.]

wavelength [nm]


450 500 550 600 650 700 750

-0.08

-0.04

0.00

0.04

0.08

abso

rban

ce c

hang

es [a

.u.]

wavelength [nm]

-10.4 ns -0.4 ns 9.6 ns 19.6 ns 29.6 ns 39.6 ns

0 2,000 4,000 6,000 8,000

0.000

0.005

0.010

0.015

0.020

0.025

abso

rban

ce c

hang

es [a

.u.]

time [ns]

DnPAm at 420 nm monoexponential fit residuals

Modell ExpDec1

Gleichung y = A1*exp(-x/t1) + y0

Chi-Quadr Reduziert

2.93687E-7


B

y0 0.00127 2.28632E-5A1 0.02056 1.4059E-4t1 8.23285E-7 8.33692E-9k 1.21465E6 12299.98878tau 5.70658E-7 5.77871E-9

0 2,000 4,000 6,000 8,000

0.000

0.005

0.010

0.015

0.020

0.025

abso

rban

ce c

hang

es [a

.u.]

time [ns]

DnPAm at 420 nm biexponential fit residuals

model biexponential




triad y0 5.5552E-4 2.93311E-5

--

x0 5.77829E-8 0.04639A1 0.01582 1708.09788t1 4.29645E-7 6.77444E-9A2 0.00658 127.42254t2 2.39667E-6 7.19146E-8

400 450 500 550 600 650 700 7500.00

0.01

0.02

0.03

0.04

0.05

norm

aliz

ed in

tens

ity [a

rb.u

.]

wavelength [nm]

Component 1(410 ns) Component 2(4,100 ns)

Figure S32. Transient absorption data of Dn‒P‒Am: (a) Spectral recovery at selected times with zoom of pulse region (b). Asterisk denotes excitation pulse artefacts due to Rayleigh scatter. Note the rapid formation of positive TA signals with characteristic signatures of pNDI‒ (475 and 610 nm) and pTARA+ (690 nm) in accordance to the spectroelectrochemical data. (c, d, e) Decay profile (at 420 nm) applying multiexponential fits: (c) Monoexponential, (d) biexponential and (e) triexponential fits with time constants of 430 ns (71%) and 2,400 ns (29%). (f) Global fit (> 100 ns) with biexponential kinetics with corresponding amplitudes. Component 1 (black curve) and 2 (red curve) shows similar spectral signatures of the fully charge separated state.

* *

a) b)

c) d)

e) f)

26

Table S2. Tabulated data of Dn‒P‒Am from the mono-, bi- and triexponential fits with associated lifetimes and standard deviation, relative amplitudes.

monoexponential biexponential triexponential Component1 823 ± 8 ns

(100%) 430 ± 7 ns (71%)

287 ± 28 ns (42%)

Component2 - 2,400 ± 72 ns (29%)

810 ± 110 ns (43%)

Component3 - - 4,800 ± 1,100 ns (15%)

χ2-reduced 2.937×E-7 4.430×E-8 4.054×E-8 Correlated R2 0.9788 0.9967 0.9971

References 1. G. R. Fulmer, A. J. M. Miller, N. H. Sherden, H. E. Gottlieb, A. Nudelman, B. M. Stoltz, J. E.

Bercaw and K. I. Goldberg, Organometallics, 2010, 29, 2176-2179. 2. A. El-Zohry, A. Orthaber and B. Zietz, J. Phys. Chem. C Nanomater. Interfaces, 2012, 116,

26144-26153. 3. Note the transmission characteristics of the "3C1 Russian Filter" given in Figure S25. 4. R. Schroot, C. Friebe, E. Altuntas, S. Crotty, M. Jäger and U. S. Schubert, Macromolecules,

2013, 46, 2039-2048. 5. J. Kübel, R. Schroot, M. Wächtler, U. S. Schubert, B. Dietzek and M. Jäger, J. Phys. Chem. C,

2015, 119, 4742-4751. 6. M. Jäger, R. J. Kumar, H. Görls, J. Bergquist and O. Johansson, Inorg. Chem., 2009, 48, 3228-

3238. 7. M. Jäger, L. Eriksson, J. Bergquist and O. Johansson, J. Org. Chem., 2007, 72, 10227-10230. 8. R. Schroot, U. S. Schubert and M. Jäger, Macromolecules, 2015, 48, 1963-1971.

Documents

Supporting Information - Royal Society of Chemistry · Supporting Information ... (Bruker Daltonics GmbH) mass spectrometer, which was equipped with an automatic syringe pump for