Supporting Information (SI)

Photocatalytic H2 production using a red-absorbing Ir(III)-

Co(III) dyad
Cédric Lentz,a Olivier Schott,b Thomas Auvray,b Garry Hanan,b* Benjamin Eliasa*
a
Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université
catholique de Louvain, Place Louis Pasteur 1, 1348 Louvain-la-Neuve (Belgium)
b
Département de Chimie, Université de Montréal, 2900 Boulevard Edouard-Montpetit, Montréal, Québec H3T
1J4 (Canada)

S1
Table of contents

Synthetic procedures............................................................................................................................. S3
Ir(III) photosensitizers ............................................................................................................ S3

Co(III) catalyst ........................................................................................................................ S9

Ir(III)-Co(III) dyad .................................................................................................................. S10

Cyclic voltammetry .............................................................................................................................. S12

Ir(III) photosensitizers .......................................................................................................... S12

Ir(III)-Co(III) dyad .................................................................................................................. S15

Photophysical measurements ............................................................................................................. S16

Photocatalyzed hydrogen production ................................................................................................. S17
Set up of gas chromatography ............................................................................................. S17

Conditions of photo-reactions ............................................................................................. S17

Various wavelengths of irradiation sources......................................................................... S18

Performance of photocatalytic systems .............................................................................. S19

Crystallographic information for Irpiq-L-Co structure......................................................................... S22

Theoretical studies .............................................................................................................................. S25
References ........................................................................................................................................... S38

S2
Synthetic procedures

Ir(III) photosensitizers

Irppy-bpy. [Ir(ppy)2Cl]2 (0.0571 mg, 0.0532 mmol) and 2,2’-bipyridine (20.0 mg, 0.128 mmol) were

suspended in ethyleneglycol (7.0 mL). The mixture was refluxed overnight under Argon. The solution

was cooled to room temperature and a saturated aqueous solution of NH4PF6 (6.0 mL) was added for

precipitation. The solid was centrifuged, washed with water (3X) and dried under reduced pressure.

HRMS (ESI): m/z calculated for [C32H24193IrN4 – PF6]+, 657.16247 ; found: 657.16221, m/z calculated for

[C22H16193IrN2 – PF6 – bpy]+, 501.09372 ; found: 501.09222. 1H NMR (CD3CN), δ/ppm: 8.53 (dd, 2H, H-3,

J3-4 = 8.1 Hz, J3-5 = 1.3 Hz), 8.12 (ddd, 2H, H-4, J4-3 = 8.1 Hz, J4-5 = 7.9 Hz, J4-6 = 1.7 Hz), 8.06 (dd, 2H, H-d,

Jd-c = 8.5 Hz, Jd-b = 1.6 Hz), 7.98 (dd, 2H, H-6, J6-5 = 5.5 Hz, J6-4 = 1.7 Hz), 7.85 (ddd, 2H, H-c, Jc-d = 8.5 Hz,

Jc-b = 7.6 Hz, Jc-a = 1.6 Hz), 7.80 (dd, 2H, H-e, Je-f = 7.8 Hz, Je-g = 1.4 Hz), 7.60 (dd, 2H, H-a, Ja-b = 5.8 Hz, Ja-

c = 1.6 Hz), 7.50 (ddd, 2H, H-5, J5-4 = 7.9 Hz, J5-6 = 5.5 Hz, J5-3 = 1.3 Hz), 7.04 (ddd, 2H, H-f, Jf-e = 7.8 Hz, Jf-

g = 7.5 Hz, Jf-h = 1.3 Hz), 7.02 (ddd, 2H, H-b, Jb-c = 7.6 Hz, Jb-a = 5.8 Hz, Jb-d = 1.6 Hz), 6.92 (ddd, 2H, H-g,

Jg-f = Jg-h = 7.5 Hz, Jg-e = 1.4 Hz), 6.28 (dd, 2H, H-h, Jh-g = 7.5 Hz, Jh-f = 1.3 Hz).

S3
Figure S1. 1H NMR spectrum of Irppy-bpy (CD3CN, 500 MHz)

Figure S2. 1H-1H dqfCOSY spectrum of Irppy-bpy (CD3CN)

S4
Irpiq-bpy. [Ir(piq)2Cl]2 (0.0322 mg, 0.0253 mmol) and 2,2’-bipyridine (9.4 mg, 0.0602 mmol) were

suspended in ethyleneglycol (3.0 mL). The mixture was refluxed overnight under Argon. The solution

was cooled to room temperature and a saturated aqueous solution of NH4PF6 (3.0 mL) was added for

precipitation. The solid was centrifuged, washed with water (3X), dried under reduced pressure and

washed again with diethylether (3X). HRMS (ESI): m/z calculated for [C40H28193IrN4 – PF6]+, 755.19144 ;

found: 755.19342, m/z calculated for [C30H20193IrN2 – PF6 – bpy]+, 601.12502 ; found: 601.12306. 1H

NMR (CD3CN), δ/ppm: 9.02 (m, 2H, H-c/H-f), 8.54 (dd, 2H, H-3, J3-4 = 8.1 Hz, J3-5 = 1.0 Hz), 8.38 (dd, 2H,

H-g, Jg-h = 8.2 Hz, Jg-i = 1.0 Hz), 8.11 (ddd, 2H, H-4, J4-3 = 8.1 Hz, J4-5 = 7.8 Hz, J4-6 = 1.1 Hz), 7.99 (m, 2H,

H-f/H-c), 7.87 (dd, 2H, H-6, J6-5 = 5.4 Hz, J6-4 = 1.1 Hz), 7.84 (m, 4H, H-d + H-e), 7.51 (d, 2H, H-b, Jb-a = 6.4

Hz), 7.46 (ddd, 2H, H-5, J5-4 = 7.8 Hz, J5-6 = 5.4 Hz, J5-3 = 1.0 Hz), 7.42 (d, 2H, H-a, Ja-b = 6.4 Hz), 7.14 (ddd,

2H, H-h, Jh-g = 8.2 Hz, Jh-i = 7.8 Hz, Jh-j = 1.1 Hz), 6.88 (ddd, 2H, H-i, Ji-h = 7.8 Hz, Ji-j = 7.6 Hz, Ji-g = 1.0 Hz),

6.31 (dd, 2H, H-j, Jj-i = 7.6 Hz, Jj-h = 1.1 Hz).

S5
Figure S3. 1H NMR spectrum of Irpiq-bpy (CD3CN, 500 MHz)

Figure S4. 1H-1H dqfCOSY spectrum of Irpiq-bpy (CD3CN)

S6
Irpiq-L

Figure S5. 1H NMR spectrum of Irpiq-L (CD3CN, 500 MHz)

S7
Figure S6. 1H-1H dqfCOSY spectrum of Irpiq-L (CD3CN)

S8
 Co(III) catalyst

Co(dmgH)2PyCl. Co(dmgH)2PyCl is synthetized by a procedure previously reported.1

CoCl2,6H2O (150 mg, 0.65 mmol), dimethylglyoxime (167 mg, 1.4 mmol) and NaOH (26.0 mg, 0.65

mmol) were dissolved in 95% ethanol (5.0 mL) and heated to 70 °C. Pyridine (51 mg, 0.65 mmol) were

then added and the resulting solution cooled to room temperature. A stream of air was then passed

through the solution for 30 min, which caused precipitation of a brown solid. The suspension was

stirred for 1 h and filtered. The precipitate was successively washed with water (10 mL), ethanol (10

mL), and diethyl ether (10 mL). The product was then extracted with acetone (15 mL) and the solution

is let to a slow evaporation (m = 130 mg, 49%). Elemental Analysis: calc. for C13H19ClCoN5O4 C= 38.68

% H=4.74 % N=17.35 %, found C=38.59 % H=4.82 % N=17.12 %.

S9
 Ir(III)-Co(III) dyad

Irpiq-L-Co

Figure S7. 1H NMR spectrum of Irpiq-L-Co (acetone-d6, 500 MHz)

S10
Figure S8. 1H-1H dqfCOSY spectrum of Irpiq-L-Co (acetone-d6)

S11
Cyclic voltammetry

Ir(III) photosensitizers

1,5

0,5
Current (normalized)

0
-2 -1,5 -1 -0,5 0 0,5
-0,5

-1

-1,5

-2
Potential (V vs. Ag/AgCl)

Figure S9. Reduction voltammogram of Irppy-bpy (10-5 M) in acetonitrile with Bu4NClO4 0.1 M as

supporting electrolyte.

1,2

0,8
Current (normalized)

0,6

0,4

0,2

0
0,5 0,7 0,9 1,1 1,3 1,5 1,7
-0,2

-0,4
Potential (V vs. Ag/AgCl)

Figure S10. Oxidation voltammogram of Irppy-bpy (10-5 M) in acetonitrile with Bu4NClO4 0.1 M as

supporting electrolyte.

S12
 2

0
-2 -1,5 -1 -0,5 0 0,5
-1
Current (normalized)

-2

-3

-4

-5
Potential (V vs. Ag/AgCl)

Irpiq-bpy

Figure S11. Reduction voltammogram of Irppy-bpy (10-5 M) in acetonitrile with Bu4NClO4 0.1 M as

supporting electrolyte.

1,2

1
Current (normalized)

0,8

0,6

0,4

0,2

0
0,5 0,7 0,9 1,1 1,3 1,5 1,7
-0,2
Potential (V vs. Ag/AgCl)

Irpiq-bpy

Figure S12. Oxidation voltammogram of Irpiq-bpy (10-5 M) in acetonitrile with Bu4NClO4 0.1 M as

supporting electrolyte.

S13
 1,5

0,5

0
-2,2 -1,7 -1,2 -0,7 -0,2 0,3 0,8
Current (normalized)

-0,5

-1

-1,5

-2

-2,5

-3
Potential (V vs. Ag/AgCl)

Figure S13. Reduction voltammogram of Irpiq-L (10-5 M) in acetonitrile with Bu4NClO4 0.1 M as

supporting electrolyte.

1,2

0,8
Current (normalized)

0,6

0,4

0,2

0
0,5 0,7 0,9 1,1 1,3 1,5 1,7 1,9
-0,2
Potential (V vs. Ag/AgCl)

Figure S14. Oxidation voltammogram of Irpiq-L (10-5 M) in acetonitrile with Bu4NClO4 0.1 M as

supporting electrolyte.

S14
 Ir(III)-Co(III) dyad

0
-2,5 -2 -1,5 -1 -0,5 0 0,5 1
Current (normalized)

-2

-4

-6

-8

-10
Potential (V vs. Ag/AgCl)

Figure S15. Reduction voltammogram of Irpiq-L-Co (10-5 M) in acetonitrile with Bu4NClO4 0.1 M as

supporting electrolyte.

1,2

0,8
Current (normiazed)

0,6

0,4

0,2

0
0,5 0,7 0,9 1,1 1,3 1,5 1,7
-0,2

-0,4
Potential (V vs. Ag/AgCl)

Figure S16. Oxidation voltammogram of Irpiq-L-Co (10-5 M) in acetonitrile with Bu4NClO4 0.1 M as

supporting electrolyte.

S15
Photophysical measurements

Table S1. Spectroscopic data of Irppy-bpy, Irpiq-bpy, Irpiq-L and Irpiq-L-Co in acetonitrile
Irppy-bpy Irpiq-bpy Irpiq-L Irpiq-L-Co

257 (512), 212 (606), 212 (749), 215 (750),

267 (487), 234 (557), 234 (639), 235 (664),
310 (227), 290 (440), 291 (596), 291 (554),
339 (96), 338 (180), 322 (374), 327 (398),
λabs [nm]
376 (64), 354 (168), 357 (180), 357 (180),
(ε[x 10² M-1 cm-1])
412 (36), 379 (109), 381 (118), 379 (111),
467 (7) 439 (67), 438 (74), 437 (62),
527 (4), 527 (5), 530 (5),
564 (1) 565 (2) 567 (2)
λmax Em[a] 599 593, 638 593, 636 593, 637

τ[b] [µs] 0.267 1.059 1.619 0.705

(39%) (43%)
1.638 2.372
(61%) (57%)

Φ[c] (Ar) 0.0215 0.0110 0.0130 0.0033

kr[d] 80.5 7.8 6.3 4.7

[x 103 s-1]
[a] Measurements in degassed acetonitrile at 298K. [b] Lifetime measured under N2 atmosphere [c]
Quantum yield was measured under air using quinine as a reference, Φref = 0.546 in 1M H2SO4 in water
under air. λexc = 366 nm [d] Radiative rate constant under inert atmosphere at 298 K (kr = Φ/τ).

S16
Photocatalyzed hydrogen production

Set up of gas chromatography

H2 rate (µL/min) = [H2 standard] (ppm)× Ar flow rate (mL/min)

100000
y = 18501x + 6217,5
90000
R² = 0,9992
80000
70000
Area of hydogen detection

60000
50000
40000
30000
20000
10000
0
0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2 2,2 2,4 2,6 2,8 3 3,2 3,4 3,6 3,8 4 4,2 4,4 4,6 4,8 5
µL of H2/min

Figure S17. Calibration curve of hydrogen flux in 10mL/min of carrier gas Argon (0 to 5 µLH2/min).

The two grey lines show the uncertainly in x of the calibration curve.

The uncertainly in x is ± 0.045 µLH2/min. The interval of confidence at 95% of the slope is 147.2

Conditions of photo-reactions

All photoreactions are performed in the same conditions:

0,5 M of electron sacrificial donor TEOA, 0,5 M HBF4 as acid source, solvent is acetonitrile.

[Irpiq-L-Co] = 0.1 mM

Dissociated systems Irpiq-bpy/Co(dmgH)2PyCl and Irppy-bpy/Co(dmgH)2PyCl are tested in the same

ratio PS/Cat (1/1) than the linked Irpiq-L-Co.

[PS] = [Cat] = 0.1 mM

S17
 Various wavelengths of irradiation sources

In the case of blue, green and red light, the interchangeable light source is composed of a 90 x

1 W LED. For yellow light, samples are tested under a 10 W LED.

120

100

80

60

40

20

0
300 350 400 450 500 550 600 650 700 750
-20

blue lamp green lamp yellow lamp red lamp

Figure S18. Emission spectra of light-emitting diodes used as irradiation sources

(blue, green, yellow, red).

Table S2. Maxima, width band of emission spectra and photon flux of used L.E.D’s.

Blue Green Yellow Red

λmax em (nm) 452 525 595 630

Δλ (nm) 150 170 85 125

Photon flux in µEinstein.min-1.cm-2 [a] 20.5 10.1 13.9 24.5

[a]
An analog power-meter PM100A (THORLABS) associated with a compact photodiode power head
with silicon detector S120C is used to evaluate the photon flux for each LEDs. Photo-diode detector is
placed at the same distance from the LED surface than the bottom of illuminated vial (0.7 cm for blue,
green and red LED panels and 1.2 cm for yellow LED).

S18
 Performance of photocatalytic systems

Table S3. Performances of Ir/Co systems for hydrogen photo-catalytic production under various
wavelengths of irradiation.

Blue LED Green LED Yellow LED Red LED

Compounds Centered at 452 nm Centered at 525 nm Centered at 595 nm Centered at 630 nm

TON TOFmax TON TOFmax TON TOFmax TON TOFmax

Irppy-bpy / 30 (0.5h) 4400 16 (4 h) 170 No detection of hydrogen No detection of hydrogen

Co(dmgH)2PyrCl

Irpiq-bpy / 70 (7h) 370 31 (22h) 58 No detection of hydrogen No detection of hydrogen

Co(dmgH)2PyrCl

Irpiq-L-Co 180 (2.3 h ) 16000 251 (3.8 h) 3500 180 (18 h) 270 78 (110 h)[a] 15[b]

TOF in mmolH2.mol-1PS.min-1 , TON in mol.H2.mol-1PS

Absolute errors of TON and TOF are estimated ± 10 % from reference systems Irppy-bpy /
Co(dmgH)2PyrCl. This system was analyzed in triplicata.
[a]
Induction time of 37 min.
[b]
A smoothing LOWESS with software Origin was applied for TOF data.

S19
 Figure S19. Hydrogen evolution of Irpiq-L-Co (green) and dissociated system Irpiq-

bpy/[Co(dmgH)2PyCl] (blue) and Irppy-bpy with Co(dmgH)2Pyr (Red). Solid line: TON, dashed line:

TOF. Irradiation centered at 452 nm (blue light)

Figure S20. Hydrogen evolution of Irpiq-L-Co. Solid line: TON, dashed line: TOF. Irradiation centered

at 595 nm (yellow light).

S20
Figure S21. Overlap of the absorption spectrum of the Ir-Co dyad (green) and the emission spectrum

of the red LED (red).

S21
Crystallographic information for Irpiq-L-Co structure

Table S4. Crystallographic information for Irpiq-L-Co structures.

Identification 1 2
CCDC Number 1515333 1515335
Empirical formula C53H45ClCoF6IrN9O4P C53H45ClCoF6IrN9O4P
Formula weight 1303.53 1303.53
Temperature/K 100 100
Crystal system monoclinic monoclinic
Space group C2/c P21/n
a/Å 43.3450(7) 17.1260(10)
b/Å 11.1091(2) 10.4445(6)
c/Å 30.4979(5) 30.4628(19)
α/° 90 90
β/° 128.3740(10) 91.457(3)
γ/° 90 90
Volume/Å3 11513.0(4) 5447.2(6)
Z 8 4
ρcalcg/cm3 1.504 1.589
μ/mm-1 7.954 8.406
F(000) 5184.0 2592.0
Crystal size/mm3 0.14 × 0.12 × 0.05 0.24 × 0.04 × 0.03
Radiation CuKα (λ = 1.54178) CuKα (λ = 1.54178)
2Θ range for data collection/° 5.2 to 144.426 5.804 to 144.292
Index ranges -53 ≤ h ≤ 53, -13 ≤ k ≤ 12, -37 ≤ l ≤ 37 -21 ≤ h ≤ 21, -12 ≤ k ≤ 12, -37 ≤ l ≤ 37
Reflections collected 167315 117808
Independent reflections 11342 [Rint = 0.0405, Rsigma = 0.0144] 10688 [Rint = 0.1045, Rsigma = 0.0491]
Data/restraints/parameters 11342/0/712 10688/323/764
Goodness-of-fit on F2 1.044 1.043
Final R indexes [I>=2σ (I)] R1 = 0.0263, wR2 = 0.0670 R1 = 0.0554, wR2 = 0.1256
Final R indexes [all data] R1 = 0.0277, wR2 = 0.0684 R1 = 0.0790, wR2 = 0.1396
Largest diff. peak/hole / e Å-3 1.84/-0.54 1.72/-1.04

S22
Figure S22. X-ray crystal structure 1 of [Irpiq-L-Co]+, atoms are represented at the 50 % probability

level. Hydrogen atoms and PF6 counteranion are omitted for clarity.

Figure S23. X-ray crystal structure 2 of [Irpiq-L-Co]+, atoms are represented at the 50 % probability

level. Hydrogen atoms and PF6 counteranion are represented.

S23
Table S5. Selected angles and bond lengths of crystal structure 1

1
Bond lengths (Å) Ir(1)–C(315) 2.004 (3)

Ir(1)–C(215) 2.009 (2)

Ir(1)–N(31) 2.047 (3)

Ir(1)–N(21) 2.049 (3)

Ir(1)–N(11) 2.141 (2)

Ir(1)–N(12) 2.133 (2)

C(19)–C(111) 1.476 (3)

C(15)–C(16) 1.481 (3)

Co(1) – N(13) 1.966 (2)

Angle (°) C(215)–Ir(1)–C(315) 87.94 (9)

N(31)–Ir(1)–C(315) 79.91 (9)

N(31)–Ir(1)–C(215) 92.95 (9)

N(21)–Ir(1)–C(315) 90.84 (9)

N(21)–Ir(1)–C(215) 79.74 (9)

N(12)–Ir(1)–C(315) 97.63 (8)

N(12)–Ir(1)–N(31) 90.57 (8)

N(12)–Ir(1)–N(21) 97.53 (8)

N(11)–Ir(1)–C(215) 98.26 (9)

N(11)–Ir(1)–N(31) 97.31 (8)

N(31)–Ir(1)–N(12) 90.57 (8)

N(21)–Ir(1)–N(11) 92.60 (8)

N(12)–Ir(1)–N(11) 76.29 (8)

N(21)–Ir(1)–N(31) 168.47 (8)

N(12)–Ir(1)–C(215) 173.87 (8)

N(11)–Ir(1)–C(315) 173.36 (8)

α, average planes angles (°) of the 5,4’ sites 31 (1)

β, average planes angles (°) of the 2,2’ sites 4.7 (1)

S24
Theoretical studies

Table S6. Representation of the orbitals LUMO+4 through to HOMO-4 with the contributions of the
different fragments of Irppy-bpy

Contour (iso 0.03 e/A3) Contribution Contour (iso 0.03 e/A3) Contribution

HOMO-4 LUMO

Ir = 30% Ir = 1%

Ppy = 67% Ppy = 2%

Bpy = 3% Bpy = 97%

HOMO-3 LUMO+1

Ir = 48% Ir = 4%

Ppy = 45% Ppy = 95%

Bpy = 7% Bpy = 1%

HOMO-2 LUMO+2

Ir = 48% Ir = 4%

Ppy = 49% Ppy = 94%

Bpy = 3% Bpy = 2%

HOMO-1 LUMO+3

Ir = 8% Ir = 1%

Ppy = 91% Ppy = 15%

Bpy = 1% Bpy = 84%

HOMO LUMO+4

Ir = 40% Ir = 1%

Ppy = 58% Ppy = 2%

Bpy = 2% Bpy = 97%

S25
Table S7. Representation of the orbitals LUMO+4 through to HOMO-4 with the contributions of the
different fragments of Irpiq-bpy

Contour (iso 0.03 e/A3) Contribution Contour (iso 0.03 e/A3) Contribution

HOMO-4 LUMO

Ir = 50% Ir = 2%

Piq = 45% Piq = 5%

Bpy = 5% Bpy = 93%

HOMO-3 LUMO+1

Ir = 36% Ir = 4%

Piq = 59% Piq = 91%

Bpy = 5% Bpy = 5%

HOMO-2 LUMO+2

Ir = 27% Ir = 3%

Piq = 72% Piq = 96%

Bpy = 1% Bpy = 1%

HOMO-1 LUMO+3

Ir = 10% Ir = 2%

Piq = 89% Piq = 10%

Bpy = 1% Bpy = 88%

HOMO LUMO+4

Ir = 37% Ir = 1%

Piq = 62% Piq = 2%

Bpy = 1% Bpy = 97%

S26
Table S8. Representation of the orbitals LUMO+4 through to HOMO-4 with the contributions of the
different fragments of Irpiq-L

Contour (iso 0.03 e/A3) Contribution Contour (iso 0.03 e/A3) Contribution

HOMO-4 LUMO

Ir = 50% Ir = 1%

Piq = 44% Piq = 2%

L = 6% L = 97%

HOMO-3 LUMO+1

Ir = 36% Ir = 4%

Piq = 59% Piq = 94%

L = 4% L = 2%

HOMO-2 LUMO+2

Ir = 26% Ir = 3%

Piq = 72% Piq = 95%

L = 2% L = 2%

HOMO-1 LUMO+3

Ir = 10% Ir = 2%

Piq = 89% Piq = 5%

L = 1% L = 93%

HOMO LUMO+4

Ir = 36% Ir = 1%

Piq = 62% Piq = 3%

L = 2% L = 96%

S27
Table S9. The 100 lowest singlet–singlet and 10 lowest singlet–triplet transitions obtained from the
TD-DFT/singlets and the TD-DFT/triplets output files for Irppy-bpy at the S0-optimized geometry.
Energy (cm-1) Wavelength (nm) Oscillation strength Major contributions

20730,06 482,39 0,0001 HOMO->LUMO (99%)

25465,34 392,69 0,0598 HOMO->L+1 (97%)

26310,61 380,07 0,0004 H-4->LUMO (17%), H-2->LUMO (82%)

26354,17 379,45 0,0017 HOMO->L+2 (91%)

26830,03 372,72 0,0293 H-1->LUMO (87%)

28154,40 355,18 0,0031 HOMO->L+3 (98%)

28174,56 354,93 0,0573 H-3->LUMO (84%)

29465,85 339,38 0,0001 H-4->LUMO (82%), H-2->LUMO (17%)

30128,84 331,91 0,0087 HOMO->L+4 (96%)

30632,94 326,45 0,007 H-5->LUMO (91%)

31177,36 320,75 0,0018 H-2->L+1 (28%), HOMO->L+5 (56%)

31272,53 319,77 0,0434 H-2->L+1 (42%), HOMO->L+5 (40%)

31362,06 318,86 0,014 H-3->L+1 (15%), H-1->L+1 (62%)

31508,05 317,38 0,0009 HOMO->L+6 (85%)

32052,47 311,99 0,0561 H-3->L+2 (10%), H-2->L+1 (10%), H-1->L+2 (70%)

32208,94 310,47 0,0127 H-3->L+1 (18%), H-2->L+2 (49%), H-1->L+1 (21%)

33188,10 301,31 0,0007 H-3->L+1 (55%), H-2->L+2 (21%)

33365,54 299,71 0,09 H-3->L+2 (61%), H-2->L+3 (13%), H-1->L+2 (13%)

33686,55 296,85 0,047 H-6->LUMO (11%), H-3->L+2 (11%), H-2->L+3 (55%)

33709,14 296,66 0,0185 H-1->L+3 (77%)

34458,42 290,20 0,0802 H-4->L+1 (61%), H-2->L+1 (10%)

34964,94 286,00 0,053 H-5->L+1 (15%), H-4->L+2 (41%), H-1->L+5 (11%)

35122,22 284,72 0,0003 H-5->L+1 (49%), H-4->L+2 (25%), H-3->L+3 (12%)

35151,26 284,48 0,1424 H-6->LUMO (38%), H-3->L+4 (15%), H-2->L+3 (14%), H-1->L+4 (19%)

35256,91 283,63 0,0167 H-5->L+1 (13%), H-3->L+3 (67%), H-1->L+3 (12%)

35586,79 281,00 0,0057 H-5->L+2 (70%)

35953,78 278,13 0,0214 H-4->L+4 (11%), H-2->L+4 (79%)

36028,79 277,56 0,1155 H-6->LUMO (13%), H-4->L+3 (14%), H-1->L+4 (52%)

36500,62 273,97 0,0143 H-7->LUMO (90%)

36812,76 271,64 0,0248 H-4->L+3 (62%), H-1->L+4 (18%)

37073,27 269,74 0,014 H-2->L+6 (31%), H-1->L+5 (37%)

37104,73 269,51 0,0001 H-2->L+5 (52%), H-1->L+6 (23%)

37540,27 266,38 0,0026 H-5->L+3 (59%)

37558,01 266,25 0,1887 H-6->LUMO (16%), H-3->L+4 (61%)

37680,61 265,39 0,3035 H-2->L+5 (13%), H-1->L+6 (35%), HOMO->L+8 (26%)

37721,74 265,10 0,0024 H-5->L+3 (18%), H-2->L+6 (10%), HOMO->L+9 (14%), HOMO->L+10 (27%)

S28
38004,84 263,12 0,1003 H-2->L+6 (30%), H-1->L+5 (28%)

38115,34 262,36 0,0033 H-8->LUMO (87%)

38560,56 259,33 0,0431 H-3->L+6 (66%), H-1->L+6 (22%)

38647,67 258,75 0,0212 H-4->L+4 (19%), H-3->L+5 (56%)

38729,94 258,20 0,2499 H-3->L+6 (19%), HOMO->L+8 (36%), HOMO->L+13 (10%)

38779,14 257,87 0,027 H-4->L+4 (60%), H-3->L+5 (16%)

39520,36 253,03 0,0042 H-9->LUMO (68%), H-5->L+4 (20%)

39813,95 251,17 0,0581 H-9->LUMO (10%), H-5->L+4 (29%), H-4->L+5 (46%)

39942,99 250,36 0,0004 H-5->L+4 (42%), H-4->L+5 (34%)

40076,88 249,52 0,0064 H-4->L+6 (65%), H-2->L+6 (10%)

40143,83 249,10 0,001 H-6->L+1 (69%)

40155,12 249,03 0,02 H-4->L+6 (20%), H-4->L+10 (11%), H-2->L+9 (10%), H-2->L+10 (29%)

40217,22 248,65 0,0151 H-6->L+1 (30%), H-3->L+9 (11%), H-3->L+10 (20%)

40472,09 247,08 0,0009 HOMO->L+7 (80%)

40677,77 245,83 0,0072 H-5->L+5 (89%)

40844,72 244,83 0 H-6->L+2 (97%)

40868,11 244,69 0,0049 H-5->L+6 (91%)

41463,35 241,18 0,0479 H-13->LUMO (12%), H-10->LUMO (10%), H-6->L+3 (68%)

41509,32 240,91 0,0037 H-8->L+2 (11%), H-7->L+1 (83%)

41818,23 239,13 0,0005 H-8->L+1 (36%), H-7->L+2 (56%)

42184,41 237,05 0,0123 H-10->LUMO (86%)

42232,00 236,79 0,0029 H-11->LUMO (63%), H-6->L+4 (20%)

42561,88 234,95 0,0051 H-12->LUMO (14%), H-11->LUMO (36%), H-6->L+4 (24%), HOMO->L+9 (11%)

42628,01 234,59 0,0695 H-6->L+4 (14%), HOMO->L+9 (36%), HOMO->L+10 (23%)

43011,13 232,50 0,0702 HOMO->L+8 (16%), HOMO->L+12 (36%), HOMO->L+13 (20%)

43361,17 230,62 0,0544 H-8->L+1 (47%), H-7->L+2 (31%)

43677,34 228,95 0,0105 H-8->L+2 (76%), H-7->L+1 (11%)

43875,75 227,92 0,0003 H-7->L+3 (88%)

43920,11 227,69 0,007 H-4->L+8 (14%), H-2->L+8 (55%)

44222,57 226,13 0,005 H-9->L+1 (66%)

44371,79 225,37 0,0048 H-9->L+2 (16%), H-1->L+8 (44%), HOMO->L+11 (18%)

44864,59 222,89 0,0005 H-9->L+2 (28%), H-3->L+8 (33%)

44943,63 222,50 0,003 H-13->LUMO (27%), H-6->L+5 (61%)

45210,60 221,19 0,0015 H-8->L+3 (59%), H-7->L+4 (31%)

45363,04 220,44 0,1297 H-12->LUMO (59%), H-6->L+4 (23%)

45528,38 219,64 0,0007 H-9->L+2 (34%), H-3->L+8 (11%), HOMO->L+11 (32%)

45622,75 219,19 0 H-6->L+6 (96%)

45721,15 218,72 0,0033 H-13->LUMO (15%), H-1->L+7 (45%)

45853,43 218,09 0,0076 H-13->LUMO (29%), H-6->L+5 (20%)

S29
 45964,73 217,56 0,0071 H-14->LUMO (22%), H-4->L+7 (10%), H-2->L+7 (53%)

46007,48 217,36 0,0029 H-8->L+3 (29%), H-7->L+4 (57%)

46230,89 216,31 0,0072 H-1->L+7 (23%), HOMO->L+12 (12%), HOMO->L+13 (20%)

46388,17 215,57 0,0338 H-10->L+1 (17%), H-3->L+7 (10%), H-1->L+9 (17%), H-1->L+10 (22%)

46567,23 214,74 0,0065 H-10->L+1 (27%), H-9->L+3 (17%), H-1->L+10 (13%)

46594,65 214,62 0 H-14->LUMO (16%), H-2->L+9 (39%), H-2->L+10 (13%)

46887,43 213,28 0,0073 H-11->L+1 (32%), H-10->L+2 (19%), H-7->L+5 (16%)

47098,75 212,32 0,0461 H-10->L+1 (14%), H-9->L+3 (59%)

47171,34 211,99 0,0077 H-14->LUMO (34%), H-2->L+7 (23%), H-2->L+9 (17%)

47324,58 211,31 0,1104 H-7->L+5 (19%), H-1->L+8 (19%), HOMO->L+11 (18%)

47331,03 211,28 0,0712 H-8->L+4 (40%), H-7->L+5 (12%), H-1->L+8 (11%)

47423,79 210,86 0,001 H-3->L+7 (39%), H-3->L+10 (10%), H-1->L+9 (17%)

47564,93 210,24 0,0495 H-3->L+7 (14%), H-3->L+9 (22%), H-1->L+10 (23%)

47626,23 209,97 0,0063 H-8->L+4 (35%), H-7->L+5 (42%)

47862,55 208,93 0,0053 H-8->L+5 (14%), H-7->L+6 (75%)

48007,73 208,30 0,0001 H-16->LUMO (77%)

48009,35 208,29 0 H-11->L+1 (33%), H-10->L+2 (47%)

48142,43 207,72 0,0019 H-15->LUMO (14%), H-11->L+2 (52%), H-10->L+1 (17%)

48165,01 207,62 0,0244 H-15->LUMO (49%), H-11->L+2 (17%)

48256,96 207,22 0,0136 H-4->L+7 (30%), H-4->L+9 (16%), H-4->L+10 (10%)

48333,58 206,90 0,0273 H-15->LUMO (10%), H-4->L+8 (33%), HOMO->L+12 (10%)

48603,78 205,75 0,0759 H-5->L+9 (11%), H-3->L+9 (14%), H-3->L+10 (16%), H-2->L+8 (11%), H-1->L+10 (12%)

48838,48 204,76 0,0232 H-8->L+5 (61%), H-7->L+6 (11%)

48904,62 204,48 0,0014 H-9->L+4 (82%)

49067,55 203,80 0,0044 H-4->L+7 (42%), H-4->L+9 (22%)

Triplets
Energy (cm-1) Wavelength (nm) Oscillation strength Major contributions

20492,93 487,97 0 HOMO->LUMO (97%)

22381,89 446,79 0 H-1->L+2 (18%), HOMO->L+1 (64%)

22742,42 439,71 0 H-1->L+1 (27%), HOMO->L+2 (51%)

23953,86 417,47 0 H-6->LUMO (37%), H-4->LUMO (16%), H-2->LUMO (31%)

25208,86 396,69 0 H-5->LUMO (11%), H-3->LUMO (48%), H-1->LUMO (33%)

26017,03 384,36 0 H-2->L+1 (22%), H-1->L+2 (14%), HOMO->L+1 (29%)

26083,16 383,39 0 H-2->L+2 (15%), H-1->L+1 (13%), HOMO->L+2 (40%)

26769,54 373,56 0 H-6->LUMO (41%), H-2->LUMO (49%)

27423,66 364,65 0 H-3->LUMO (33%), H-1->LUMO (62%)

27500,28 363,63 0 HOMO->L+3 (74%), HOMO->L+5 (11%)

S30
Table S10. The 100 lowest singlet–singlet and 10 lowest singlet–triplet transitions obtained from the
TD-DFT/singlets and the TD-DFT/triplets output files for Irpiq-bpy at the S0-optimized geometry.
Energy (cm-1) Wavelength (nm) Oscillation strength Major contributions

20614,72 485,09 0,0023 HOMO->LUMO (97%)

21960,86 455,36 0,0968 HOMO->L+1 (96%)

22972,28 435,31 0,0009 HOMO->L+2 (97%)

24966,89 400,53 0,0293 H-1->LUMO (96%)

25502,44 392,12 0,0007 H-4->LUMO (11%), H-2->LUMO (83%)

26640,49 375,37 0,0197 H-1->L+1 (88%)

27001,83 370,35 0,042 H-2->L+1 (44%), H-1->L+2 (36%)

27618,84 362,07 0,0861 H-2->L+1 (33%), H-1->L+2 (54%)

27856,78 358,98 0,0674 H-3->LUMO (79%)

28217,31 354,39 0,0069 H-4->LUMO (21%), HOMO->L+3 (63%)

28289,09 353,49 0,0262 H-2->L+2 (54%), HOMO->L+3 (16%)

28397,17 352,15 0,0033 H-4->LUMO (61%), HOMO->L+3 (18%)

29440,04 339,67 0,0172 H-3->L+1 (68%)

29753,79 336,09 0,1394 H-3->L+2 (83%)

29898,97 334,46 0,1481 H-4->L+1 (53%), H-2->L+1 (12%), HOMO->L+4 (20%)

30073,19 332,52 0,0581 H-4->L+1 (21%), HOMO->L+4 (61%)

30168,36 331,47 0,0004 H-5->LUMO (75%)

30582,12 326,99 0,0506 H-4->L+2 (62%)

31152,36 321,00 0,0106 H-5->L+1 (67%)

31543,54 317,02 0,0472 H-5->L+2 (23%), HOMO->L+5 (16%), HOMO->L+6 (46%)

31825,83 314,21 0,0011 H-5->L+1 (10%), HOMO->L+5 (72%), HOMO->L+6 (10%)

31950,04 312,99 0,0581 H-5->L+2 (57%), HOMO->L+6 (34%)

32331,54 309,30 0,0084 H-1->L+3 (92%)

33095,35 302,16 0,0459 H-2->L+3 (78%)

33934,97 294,68 0,0108 H-6->LUMO (21%), H-1->L+4 (59%)

33955,94 294,50 0,0096 H-6->LUMO (69%), H-1->L+4 (21%)

34510,04 289,77 0,0012 H-7->LUMO (54%), H-7->L+1 (16%), H-6->L+2 (18%)

34576,99 289,21 0,0029 H-7->L+2 (12%), H-6->L+1 (62%)

34914,93 286,41 0,0032 H-7->LUMO (34%), H-7->L+1 (16%), H-6->L+2 (13%), H-2->L+4 (21%)

34979,46 285,88 0,1786 H-8->LUMO (27%), H-4->L+3 (11%), H-1->L+5 (12%)

35048,02 285,32 0,0175 H-7->LUMO (10%), H-2->L+4 (60%)

35273,04 283,50 0,3871 H-8->LUMO (15%), H-1->L+5 (42%)

35311,76 283,19 0,0318 H-4->L+3 (13%), H-3->L+3 (56%)

35642,45 280,56 0,0198 H-3->L+3 (13%), H-1->L+6 (43%)

36240,10 275,94 0,079 H-8->LUMO (16%), H-4->L+3 (54%), H-3->L+4 (10%)

36373,99 274,92 0,0008 H-7->L+1 (45%), H-6->L+2 (47%)

S31
36421,58 274,56 0,0089 H-11->LUMO (13%), H-9->LUMO (62%)

36507,07 273,92 0,0016 H-8->L+1 (24%), H-2->L+6 (24%), HOMO->L+7 (10%)

36581,28 273,36 0,0643 H-8->L+1 (20%), H-7->L+2 (23%), H-2->L+6 (28%)

36603,05 273,20 0,0059 H-8->L+1 (45%), H-7->L+2 (31%)

36730,49 272,25 0,0414 H-2->L+5 (64%)

36884,54 271,12 0,0251 H-7->L+2 (16%), HOMO->L+7 (55%)

37270,07 268,31 0,034 H-8->L+2 (50%), H-3->L+4 (25%)

37347,50 267,76 0,015 H-8->L+2 (11%), H-5->L+3 (11%), HOMO->L+8 (54%)

37387,02 267,47 0,0931 H-8->L+2 (31%), H-3->L+4 (39%)

37556,40 266,27 0,0194 H-5->L+3 (53%), HOMO->L+8 (17%)

37604,79 265,92 0,0037 HOMO->L+10 (14%), HOMO->L+11 (14%), HOMO->L+12 (33%)

37799,98 264,55 0,0396 H-5->L+3 (14%), H-4->L+4 (69%)

38119,38 262,33 0,0908 HOMO->L+9 (53%)

38203,26 261,76 0,0338 H-12->LUMO (38%), H-10->LUMO (40%)

38287,14 261,18 0,0144 H-11->L+1 (14%), H-9->L+1 (57%)

38760,59 257,99 0,018 H-3->L+5 (88%)

38831,56 257,52 0,009 H-12->L+1 (19%), H-11->L+2 (12%), H-9->L+2 (47%)

38963,84 256,65 0,0121 H-3->L+6 (74%)

39302,59 254,44 0,0378 H-5->L+4 (20%), H-4->L+5 (26%), H-4->L+6 (13%)

39364,70 254,03 0,0319 H-5->L+4 (26%), H-4->L+6 (34%)

39407,44 253,76 0,0138 H-5->L+4 (28%), H-4->L+5 (28%), H-4->L+6 (12%)

39463,10 253,40 0,0109 H-12->LUMO (26%), H-11->LUMO (19%), H-10->LUMO (25%), H-5->L+4 (14%)

39688,12 251,96 0,0159 H-12->LUMO (14%), H-11->LUMO (47%), H-9->LUMO (11%)

39805,07 251,22 0,0089 H-3->L+12 (10%), H-1->L+12 (13%)

40095,43 249,40 0,0307 H-12->L+1 (11%), H-4->L+6 (12%)

40145,44 249,09 0,0053 H-12->L+1 (18%)

40451,12 247,21 0,0074 H-1->L+7 (12%), HOMO->L+10 (47%)

40486,61 247,00 0,0065 H-5->L+6 (18%), H-1->L+7 (15%)

40560,01 246,55 0,0084 H-12->L+1 (13%), H-5->L+5 (33%)

40685,83 245,79 0,0021 H-13->LUMO (83%)

40747,94 245,41 0,018 H-12->L+2 (25%), H-1->L+7 (12%), HOMO->L+11 (15%)

40797,14 245,12 0,0205 H-12->L+2 (15%), H-5->L+5 (10%), H-5->L+6 (19%), H-1->L+7 (26%)

40908,44 244,45 0,0559 H-6->L+3 (15%), H-1->L+8 (39%)

41106,05 243,27 0,026 H-6->L+3 (29%), H-5->L+5 (26%), H-1->L+8 (18%)

41287,52 242,20 0,0152 H-11->L+1 (13%), H-7->L+3 (14%), H-5->L+6 (28%)

41585,14 240,47 0,0118 H-2->L+7 (13%), HOMO->L+11 (10%)

41644,82 240,13 0,0413 H-13->L+1 (12%), H-10->L+1 (31%), H-6->L+3 (14%)

41769,84 239,41 0,0101 H-7->L+3 (15%), H-2->L+8 (11%)

41780,33 239,35 0,023 H-8->L+3 (33%)

S32
 41851,30 238,94 0,0954 H-13->L+1 (12%), H-10->L+2 (10%), H-8->L+3 (36%)

41961,80 238,31 0,0198 H-13->L+1 (24%), H-11->L+1 (13%), H-10->L+2 (13%), H-2->L+7 (10%)

42171,50 237,13 0,021 H-13->L+1 (14%), H-11->L+2 (29%), H-2->L+7 (13%)

42265,87 236,60 0,0179 H-2->L+8 (24%), H-1->L+9 (14%), HOMO->L+11 (10%)

42286,04 236,48 0,0203 H-7->L+3 (35%), H-1->L+9 (11%)

42596,56 234,76 0,0145 H-13->L+2 (36%), H-2->L+8 (12%), H-1->L+9 (15%)

42720,77 234,08 0,0326 H-8->L+4 (54%)

42809,49 233,59 0,0111 H-13->L+2 (44%), H-1->L+9 (10%)

42986,93 232,63 0,0247 H-2->L+7 (12%), H-2->L+8 (16%), H-2->L+9 (18%), HOMO->L+13 (13%)

43044,20 232,32 0,0377 H-4->L+9 (11%), H-2->L+9 (12%), HOMO->L+13 (16%)

43333,75 230,77 0,0131 H-6->L+4 (78%)

43532,97 229,71 0,1086 H-3->L+7 (21%), H-3->L+8 (24%)

43695,09 228,86 0,0465 H-4->L+8 (24%)

43949,15 227,54 0,0589 H-3->L+8 (18%), H-2->L+9 (10%)

43985,45 227,35 0,0068 H-7->L+4 (84%)

44052,39 227,00 0,0007 H-11->L+3 (17%), H-9->L+3 (71%)

44370,98 225,37 0,0084 H-3->L+7 (39%), H-3->L+8 (12%), H-3->L+9 (12%)

44432,28 225,06 0,0076 H-1->L+10 (66%), H-1->L+11 (10%)

44952,50 222,46 0,0066 H-3->L+9 (17%), H-2->L+10 (17%)

45071,87 221,87 0,0123 H-3->L+8 (13%), H-1->L+11 (41%)

45230,77 221,09 0,0378 H-15->LUMO (10%), H-14->LUMO (16%), H-6->L+5 (23%), H-2->L+10 (12%)

45280,77 220,84 0,0856 H-6->L+6 (33%), H-4->L+7 (16%)

45325,13 220,63 0,0037 H-14->LUMO (12%), H-12->L+3 (14%), H-10->L+3 (11%), H-9->L+4 (29%)

45348,52 220,51 0,0195 H-15->LUMO (19%), H-14->LUMO (11%), H-8->L+5 (10%), H-6->L+5 (15%)

45434,82 220,10 0,0143 H-14->LUMO (35%), H-8->L+5 (12%)

Triplets
Energy (cm-1) Wavelength (nm) Oscillation strength Major contributions

18120,05 551,87 0 H-2->L+1 (14%), H-1->L+2 (31%), HOMO->L+1 (42%)

18297,49 546,52 0 H-2->L+2 (16%), H-1->L+1 (39%), HOMO->L+2 (33%)

20397,76 490,25 0 HOMO->LUMO (91%)

21777,78 459,18 0 H-2->L+1 (24%), H-1->L+2 (14%), HOMO->L+1 (45%)

22261,71 449,20 0 H-2->L+2 (18%), H-1->L+1 (10%), HOMO->L+2 (57%)

23847,39 419,33 0 H-8->LUMO (30%), H-4->LUMO (21%), H-2->LUMO (27%)

24133,72 414,36 0 H-3->LUMO (14%), H-1->LUMO (68%)

26012,19 384,44 0 H-8->LUMO (32%), H-2->LUMO (51%)

26091,23 383,27 0 H-4->L+1 (12%), H-2->L+1 (17%), H-2->L+2 (10%), H-1->L+1 (11%), H-1->L+2 (14%)

26295,29 380,30 0 H-4->L+1 (14%), H-2->L+1 (13%), H-2->L+2 (12%), H-1->L+1 (11%)

S33
Table S11. The 100 lowest singlet–singlet and 10 lowest singlet–triplet transitions obtained from the
TD-DFT/singlets and the TD-DFT/triplets output files for Irpiq-L at the S0-optimized geometry.
Energy (cm-1) Wavelength (nm) Oscillation strength Major contributions

19368,60 516,30 0,001 HOMO->LUMO (98%)

22009,26 454,35 0,0957 HOMO->L+1 (97%)

22998,09 434,82 0,0001 HOMO->L+2 (95%)

23565,10 424,36 0,0179 H-1->LUMO (95%)

24251,48 412,35 0,0008 H-2->LUMO (86%)

26565,48 376,43 0,0622 H-3->LUMO (75%), H-1->L+1 (12%)

26675,98 374,87 0,0055 H-3->LUMO (11%), H-1->L+1 (77%)

26901,01 371,73 0,0156 H-4->LUMO (50%), HOMO->L+3 (21%)

27070,39 369,41 0,0374 H-4->LUMO (10%), H-2->L+1 (37%), H-1->L+2 (30%)

27184,11 367,86 0,0049 H-4->LUMO (27%), HOMO->L+3 (67%)

27636,59 361,84 0,0805 H-2->L+1 (33%), H-1->L+2 (54%)

28297,96 353,38 0,0435 H-2->L+2 (70%)

28794,80 347,28 0,0047 H-5->LUMO (86%)

29394,07 340,20 0,0137 H-3->L+1 (54%), HOMO->L+4 (24%)

29602,16 337,81 0,0564 H-3->L+1 (16%), H-3->L+2 (10%), HOMO->L+4 (61%)

29778,80 335,81 0,0646 H-3->L+2 (71%)

29975,60 333,60 0,2104 H-4->L+1 (67%)

30547,44 327,36 0,0476 H-5->L+1 (10%), H-4->L+2 (63%)

31117,68 321,36 0,0101 H-5->L+1 (33%), H-4->L+2 (12%), H-1->L+3 (35%)

31181,39 320,70 0,0039 H-5->L+1 (33%), H-1->L+3 (54%)

31445,94 318,01 0,0552 H-5->L+2 (13%), HOMO->L+5 (66%)

31757,27 314,89 0,1669 H-6->LUMO (30%), H-2->L+3 (35%)

31921,00 313,27 0,0277 HOMO->L+6 (66%)

31943,59 313,05 0,0735 H-5->L+2 (56%), HOMO->L+5 (14%), HOMO->L+6 (16%)

32356,54 309,06 0,2784 H-6->LUMO (49%), H-2->L+3 (36%)

32543,66 307,28 0,0934 H-7->LUMO (86%)

32988,88 303,13 0,0082 H-9->LUMO (90%)

33202,62 301,18 0,0014 H-8->LUMO (94%)

33435,71 299,08 0,011 HOMO->L+7 (85%)

33700,26 296,73 0,0554 H-1->L+4 (82%)

34247,91 291,99 0,0175 H-3->L+3 (81%)

34445,52 290,31 0,0308 H-8->L+2 (11%), H-7->L+1 (46%), H-2->L+4 (13%)

34531,82 289,59 0,0327 H-2->L+4 (57%)

34656,03 288,55 0,0322 H-10->LUMO (67%), H-4->L+3 (10%)

34685,07 288,31 0,0358 H-10->LUMO (24%), H-8->L+1 (18%), H-7->L+2 (17%), H-4->L+3 (10%)

34750,40 287,77 0,0882 H-8->L+1 (15%), H-6->L+1 (10%), H-4->L+3 (33%)

S34
34985,10 285,84 0,053 H-6->L+1 (46%), H-4->L+3 (16%), H-1->L+6 (10%)

35295,63 283,32 0,1004 H-13->LUMO (12%), H-11->LUMO (57%), H-1->L+6 (11%)

35360,96 282,80 0,2805 H-7->L+1 (11%), H-6->L+1 (19%), H-1->L+5 (15%), H-1->L+6 (24%)

35493,23 281,74 0,0481 H-6->L+2 (15%), H-1->L+5 (29%), H-1->L+6 (12%)

35942,49 278,22 0,0028 H-6->L+2 (71%)

36343,34 275,15 0,0011 H-8->L+1 (46%), H-7->L+2 (49%)

36446,58 274,37 0,0097 H-5->L+3 (83%)

36480,46 274,12 0,0221 H-2->L+5 (38%), H-2->L+6 (19%), H-1->L+6 (19%)

36557,89 273,54 0,0346 H-8->L+2 (65%), H-7->L+1 (13%)

36624,83 273,04 0,0567 H-3->L+4 (63%)

36672,42 272,68 0,0208 H-2->L+5 (22%), H-2->L+6 (41%), H-1->L+5 (12%)

36891,80 271,06 0,0167 H-8->L+2 (12%), HOMO->L+9 (56%)

36995,85 270,30 0,0313 H-14->LUMO (26%), H-12->LUMO (50%), H-3->L+4 (10%)

37121,67 269,38 0,0028 H-1->L+7 (79%)

37281,37 268,23 0,0243 H-4->L+4 (71%)

37443,48 267,07 0,0083 HOMO->L+8 (10%), HOMO->L+10 (43%), HOMO->L+12 (10%), HOMO->L+14 (15%)

37597,53 265,97 0,0008 HOMO->L+8 (65%), HOMO->L+10 (25%)

37688,68 265,33 0,0072 HOMO->L+8 (23%), HOMO->L+10 (17%), HOMO->L+12 (20%), HOMO->L+14 (19%)

37928,22 263,66 0,0141 H-14->LUMO (35%), H-13->LUMO (16%), H-12->LUMO (16%)

38098,41 262,48 0,0478 H-11->L+1 (16%), H-9->L+1 (29%), HOMO->L+11 (21%)

38153,25 262,10 0,0549 H-13->LUMO (12%), H-9->L+1 (12%), HOMO->L+11 (35%)

38247,62 261,45 0,011 H-14->LUMO (10%), H-13->LUMO (37%), H-11->LUMO (11%), H-9->L+1 (10%)

38321,82 260,95 0,0076 H-2->L+7 (74%)

38499,26 259,75 0,0097 H-11->L+1 (27%), H-9->L+1 (31%)

38655,73 258,69 0,0459 H-15->LUMO (13%), H-6->L+3 (29%), H-3->L+5 (12%)

38762,20 257,98 0,0118 H-6->L+3 (12%), H-3->L+5 (35%), H-3->L+6 (17%)

38788,01 257,81 0,0017 H-10->L+1 (75%), H-10->L+2 (15%)

38846,08 257,43 0,0071 H-14->L+1 (12%), H-13->L+2 (10%), H-11->L+2 (32%), H-9->L+2 (18%)

38883,18 257,18 0,0088 H-5->L+4 (46%), H-3->L+6 (32%)

38968,68 256,62 0,0118 H-5->L+4 (24%), H-3->L+5 (21%), H-3->L+6 (33%)

39263,88 254,69 0,042 H-12->L+1 (10%), H-4->L+5 (60%)

39407,44 253,76 0,0023 H-16->LUMO (18%), H-9->L+2 (21%), H-4->L+6 (31%)

39428,41 253,62 0,0074 H-16->LUMO (59%), H-9->L+2 (10%)

39480,84 253,29 0,0062 H-9->L+2 (28%), H-4->L+6 (25%)

39854,27 250,91 0,0116 H-1->L+12 (13%), H-1->L+14 (12%)

39910,73 250,56 0,0024 H-10->L+1 (15%), H-10->L+2 (79%)

39959,13 250,26 0,0031 H-7->L+3 (57%)

40055,11 249,66 0,0406 H-15->LUMO (23%), H-6->L+3 (12%)

40157,54 249,02 0,0073 H-15->LUMO (18%)

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 40245,45 248,48 0,0401 H-15->LUMO (12%), H-14->L+1 (21%), H-11->L+2 (10%), H-7->L+3 (12%)

40349,50 247,83 0,0035 H-3->L+7 (54%)

40461,61 247,15 0,0001 H-5->L+5 (22%)

40574,53 246,46 0,0042 H-9->L+3 (57%)

40606,79 246,26 0,0235 H-14->L+1 (12%), H-5->L+6 (34%), H-1->L+9 (10%)

40680,99 245,82 0,0099 H-5->L+5 (14%), H-1->L+9 (44%)

40767,29 245,29 0,0353 H-8->L+3 (38%), H-5->L+5 (19%)

40824,56 244,95 0,0249 H-14->L+2 (35%), H-8->L+3 (16%)

40952,80 244,18 0,0273 H-6->L+4 (10%), H-4->L+7 (46%)

41006,84 243,86 0,0002 H-1->L+8 (95%)

41051,20 243,60 0,0358 H-2->L+9 (11%), H-1->L+10 (46%)

41234,29 242,52 0,0232 H-6->L+4 (30%)

41378,66 241,67 0,0322 H-6->L+4 (16%), H-4->L+7 (19%)

41512,55 240,89 0,068 H-12->L+1 (11%), H-5->L+6 (22%)

41598,85 240,39 0,0074 H-10->L+3 (79%)

41645,63 240,12 0,015 H-16->L+1 (12%), H-13->L+2 (12%), H-12->L+1 (17%), H-1->L+10 (10%)

41795,65 239,26 0,019 H-16->L+1 (28%), H-12->L+2 (14%)

41891,63 238,71 0,015 H-2->L+9 (13%), H-2->L+10 (13%)

41944,06 238,41 0,0138 H-14->L+2 (11%), H-13->L+1 (11%), H-12->L+2 (23%), H-2->L+9 (11%)

42148,92 237,25 0,004 H-16->L+1 (30%), H-13->L+2 (25%)

42287,65 236,48 0,0058 H-2->L+10 (16%), H-1->L+11 (33%), HOMO->L+12 (11%), HOMO->L+14 (10%)

42377,98 235,97 0,0004 H-5->L+7 (80%)

42436,86 235,64 0,0013 H-2->L+8 (86%)

42629,63 234,58 0,0124 H-16->L+2 (23%), H-2->L+10 (20%), H-1->L+11 (12%)

42791,75 233,69 0,0149 H-16->L+2 (40%), H-7->L+4 (15%)

Triplets
Energy (cm-1) Wavelength (nm) Oscillation strength Major contributions

18121,66 551,83 0 H-2->L+1 (15%), H-1->L+2 (31%), HOMO->L+1 (42%)

18302,33 546,38 0 H-2->L+2 (16%), H-1->L+1 (41%), HOMO->L+2 (33%)

19191,16 521,07 0 HOMO->LUMO (93%)

21814,88 458,40 0 H-2->L+1 (24%), H-1->L+2 (13%), HOMO->L+1 (46%)

22306,07 448,31 0 H-2->L+2 (18%), HOMO->L+2 (52%)

22406,08 446,31 0 H-6->LUMO (35%), H-4->LUMO (19%), H-2->LUMO (16%)

22990,83 434,96 0 H-3->LUMO (11%), H-1->LUMO (74%)

24473,28 408,61 0 H-6->LUMO (25%), H-2->LUMO (65%)

25571,00 391,07 0 H-3->LUMO (57%), H-1->LUMO (16%)

26146,88 382,45 0 H-4->L+1 (10%), H-3->L+1 (10%), H-2->L+1 (16%), H-1->L+1 (13%), H-1->L+2 (17%)

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Figure S24. Experimental spectra and calculated transitions for in Irppy-bpy (upper), Irpiq-bpy

(middle) and Irpiq-L (lower) in CH3CN

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References

1 Razavet, M.; Artero, V.; Fontecave, M. Proton Electroreduction Catalyzed by Cobaloximes

- Functional Models for Hydrogenases. Inorg. Chem. 2005, 44, 4786.
2 Harris, D. C. Quantitative chemical analysis; W. H. Freeman and Company: New York, NY,
2007.

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