Supporting information for:

Synthesis, Structure, Electrochemical and Spectroscopic Properties of Hetero-

Bimetallic Ru(II)/Fe(II)-Alkynyl Organometallic Complexes

Amit Sil,a Utsav Ghosh,a Vipin Kumar Mishra,a Sabyashachi Mishra* a and Sanjib K Patra*a
a
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur-721302, WB,
INDIA, E-mail: [email protected]; Tel: +913222283338

1. Synthesis and Characterization 2-24

1a. Syntheses 2-3
1b. NMR Spectra 4-16
1c. FTIR spectra 17-20
1d. Mass spectrometry 21-23
1e CHN analysis 24
2. Crystallographic data and refinement parameters 25-27
3. Photophysical studies 28
4. Electrochemical characterization 28-30
5 Theoretical studies 30-34
6. References 35

1
 1. Synthesis and Characterization
1a. Synthesis

General procedure for the synthesis of ligands:1 To a solution of 2-acetyl pyridine (1.86 mL,
16.6 mmol) and potassium hydroxide (0.93 g, 16.6 mmol) in absolute EtOH (40 mL), an
aryldehyde (8.3 mmol) was added and stirred for 5 mints. Then 35 mL of NH 4OH was added to
the reaction mixtures and allowed to stir at ambient temperature for overnight. The precipitates
were filtered off and washed sequentially with H2O and cold MeOH for three times. The crude
products were purified by recrystallization from anhydrous ethanol to afford needle like white
crystalline product.

4'(Phenyl)-2,2':6',2''-terpyridine (L1): According to the general protocol for the synthesis of

ligands, 2-acetyl pyridine (1.86 mL, 16.6 mmol), 4-fluorobenzaldehyde (0.9 mL, 8.3 mmol) and
potassium hydroxide (0.93 g, 16.6 mmol) were reacted in presence of 35 mL of NH4OH and 40
mL of EtOH to yield compound L1 as white solid. Recrystallization from anhydrous ethanol
afforded compound L1 as white needle like crystalline product (1.55 g, 57%). 1H NMR (CDCl3,
400 MHz): δ 7.17-7.22 (m, 2H, Aryl), 7.34-7.37 (m, 3H, Aryl), 7.86-7.90 (m, 4H, Py), 8.66-8.73
(m, 6H, Py); 13
C{1H} NMR (CDCl3, 100 MHz): δ 115.9, 116.2, 118.9, 121.5, 124.0,129.3,
137.0, 149.3, 156.1, 156.3; LCMS ESI+(m/z) = 328.4 ([M+H]+)

4'(4-Methylphenyl)-2,2':6',2''-terpyridine (L2): According to the general protocol for the

synthesis of ligands, 2-acetyl pyridine (1.86 mL, 16.6 mmol), 4-methylbenzaldehyde (0.98 mL,
8.3 mmol) and potassium hydroxide (0.93 g, 16.6 mmol) were reacted in presence of 35 mL of
NH4OH and 40 mL of EtOH to yield compound L2 as white solid. Recrystallization from
anhydrous ethanol afforded compound L2 as white needle like crystalline product (1.60 g, 60%).
1
H NMR (CDCl3, 400 MHz): δ 2.44 (s, 3H, methyl), 7.31-7.37 (m, 4H, Aryl), 7.83 (d, J=8 Hz,
2H, Py), 7.86-7.9 (m, 2H, Py), 8.68 (d, J=8 Hz, 2H, Py), 8.73-8.74 (m, 4H, Py); 13C{1H} NMR
(CDCl3, 100 MHz): δ 21.5, 118.8, 121.6, 123.9, 127.3, 129.8, 135.6, 137.1, 139.3, 149.2, 150.3,
155.9, 156.5; LCMS ESI+ (m/z) = 310.4 ([M+H]+)

4'(4-Fluorophenyl)-2,2':6',2''-terpyridine (L3): According to the general protocol for the

synthesis of ligands, 2-acetyl pyridine (1.86 mL, 16.6 mmol), benzaldehyde (0.84 mL, 8.3 mmol)
and potassium hydroxide (0.93 g, 16.6 mmol) were reacted in presence of 35 mL of NH4OH and
40 mL of EtOH to yield compound L3 as white solid. Recrystallization from anhydrous ethanol

2
afforded compound L3 as white needle like crystalline product (1.41 g, 55%). 1H NMR (CDCl3,
400 MHz): δ 7.34-7.37 (m, 2H, Aryl), 7.44-7.54 (m, 2H, Aryl), 7.86-7.92 (m, 4H, Py), 8.68 (d,
J=8 Hz, 2H, Py), 8.73-8.75 (m, 4H, Py); 13
C{1H} NMR (CDCl3, 100 MHz): δ 118.9, 121.4,
123.8, 127.4, 128.9, 129.0, 136.9, 138.5, 149.2, 150.4, 155.9, 156.3; LCMS ESI+ (m/z) = 328.4
([M+H]+)

4'(4-aminophenyl)-2,2':6',2''-terpyridine (L4): According to the general protocol for the

synthesis of ligands, 2-acetyl pyridine (1.86 mL, 16.6 mmol), 4-
(dimethylamino)phenylbenzaldehyde (2.92 g, 8.3 mmol) and potassium hydroxide (0.93 g, 16.6
mmol) were reacted in presence of 35 mL of NH4OH and 40 mL of EtOH to yield compound L4
as yellow solid. Recrystallization from anhydrous ethanol afforded compound L4 as yellow
needle like crystalline product (1.52 g, 52%). 1H NMR (400 MHz, CDCl3) δ 3.04 (s, 6H, CH3),
6.84 (d, J = 8.8 Hz, 2H, Aryl), 7.34-7.30 (m, 2H, Aryl), 7.92–7.84 (m, 4H, Py), 8.66 (d, J = 8.0
Hz, 2H, Py), 8.70 (s, 2H, Py), 8.72 (d, J = 4.8 Hz, 2H, Py); 13C{1H} NMR (100 MHz, CDCl3) δ
156.8, 155.8, 151.3, 150.2, 149.2, 136.9, 128.2, 125.7, 123.7, 121.5, 117.7, 112.4, 40.5; LCMS
ESI+ (m/z) = 353.1 ([M+H]+)

Synthesis of Ethynylferrocene2: To a solution of (2-Formyl-1-chlorovinyl)ferrocene 10 (0.952

g, 3.46 mmol) in 30 mL of dioxane, a solution of 1N NaOH (20 mL) was added, keeping it in
argon atmosphere. The solution mixture was heated to reflux for 30 min before poured into 50
mL of cold water. After acidification with HCl, the reddish black mixture solution was extracted
with DCM, washed with water and brine and finally dried over MgSO4. The solvent was
removed by rotary evaporation. It was purified using silica gel column chromatography by 20%
ethylacetate-hexane mixture to afford ethynylferrocene as orange-yellow solid with 0.575 g
(72%).1H NMR (400 MHz, CDCl3,) δ (ppm): 4.46 (s, 2H, Cp), 4.22-4.20 (m, 7H, Cp), 2.72 (s,
1H, Fc-C≡CH; 13C{1H} NMR (100 MHz, CDCl3,) δ (ppm): 82.8, 73.8, 71.9, 70.2, 68.9, 64.0.

3
 1.b NMR Spectra

Figure S1a: 1H NMR (400MHz, CDCl3) spectrum of Ethynylferrocene.

Figure S1b: 13C{1H} NMR (100MHz, CDCl3) spectrum of Ethynylferrocene.

4
 Figure S2a: 1H NMR (600 MHz, CDCl3) spectrum of 1.

Figure S2b: 13C{1H}NMR (150 MHz, CDCl3) spectrum of 1.

5
Figure S2c: 31P{1H} NMR (162 MHz, CDCl3) spectrum of 1.

Figure S3a: 1H NMR (400 MHz, CDCl3) spectrum of 2.

6
Figure S3b: 13C{1H}NMR (100 MHz, CDCl3) spectrum of 2.

Figure S3c: 31P{1H} NMR (162 MHz, CDCl3) spectrum of 2.

7
 Figure S4a: 1H NMR (600 MHz, CDCl3) spectrum of 3.

Figure S4b: 13C{1H}NMR (150 MHz, CDCl3) spectrum of 3.

8
Figure S4c: 31P{1H} NMR (162 MHz, CDCl3) spectrum of 3.

Figure S5a: 1H NMR (600 MHz, CDCl3) spectrum of 4.

9
Figure S5b: 13C{1H}NMR (125 MHz, CDCl3) spectrum of 4.

Figure S5c: 31P{1H} NMR (162 MHz, CDCl3) spectrum of 4.

10
 Figure S6a: 1H NMR (600 MHz, CDCl3) spectrum of 5.

Figure S6b: 13C{1H}NMR (125 MHz, CDCl3) spectrum of 5.

11
Figure S6c: 31P{1H} NMR (162 MHz, CDCl3) spectrum of 5.

Figure S7a: 1H NMR (600 MHz, CDCl3) spectrum of 6.

12
Figure S7b: 13C{1H}NMR (100 MHz, CDCl3) spectrum of 6.

Figure S7c: 31P{1H} NMR (162 MHz, CDCl3) spectrum of 6.

13
 Figure S8a: 1H NMR (600 MHz, CDCl3) spectrum of 7.

Figure S8b: 13C{1H}NMR (100 MHz, CDCl3) spectrum of 7.

14
 Figure S8c: 31P{1H} NMR (162 MHz, CDCl3) spectrum of 7.

Figure S9a: 1H NMR (600 MHz, CDCl3) spectrum of 8 (Fc = Ferrocenyl).

15
Figure S9b: 13C{1H}NMR (100 MHz, CDCl3) spectrum of 8.

Figure S9c: 31P{1H} NMR (162 MHz, CDCl3) spectrum of 8.

16
 1c. FTIR data (measured as KBr pellets)
74.0

72

70
3057.51
68 1221.81
1160.40
1090.89 790.25 557.80
66
3447.70 1435.87 750.08
64

62

60
699.28
517.60
58
%T
56

54

52

50

48

46

44
842.36

41.7
4400.0 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

Figure S10. FTIR spectrum of 1.

74.0

70

3056.99 1602.05
65 1221.67
3447.65
1405.97 1160.38

1090.86
60 790.11 557.79
742.46
1435.50

55

699.07
%T 50 517.23

45

40

35

844.56
30
28.7
4400.0 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

Figure S11. FTIR spectrum of 2.

17
 74.0

72

70 1189.15
1607.60
68 3059.53

3447.81 1092.50
66
789.33 557.59
64
1435.34 742.80 499.51
62

60

58
%T 699.28
56 516.29

54

52

50

48

46

44
840.16
42
41.1
4400.0 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

Figure S12. FTIR spectrum of 3.

75.4
75

74

73

72 3053.27

1433.97
71 1599.78 745.45
1174.451091.35
1223.49
70

3447.83
69 698.19 517.80
%T
68

67

66

65

64

63

841.37
61.9
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

Figure S13: FTIR spectrum of 4.

18
 74.6
74

73

2922.05
72
2070.58
3050.00 1429.93
1619.25
71 1091.05

70 2366.83

69

68 3447.55
516.93

67 697.07

%T
66

65

64

63

62

61

60

59 840.16
58.6
4400.0 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

Figure S14: FTIR spectrum of 5.

73.9

73

72

71

70 3058.82 1432.04 1091.26

1599.44
69
2851.47
2063.62
68
3436.11 2923.90

67 749.97
515.87
66

697.32
%T 65

64

63

62

61

60

59

58
842.36

56.6
4400.0 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

Figure S15: FTIR spectrum of 6.

19
 74.5

72

2375.00 2069.65
70
3053.01 1603.13
3447.16 1233.38 1091.36
68
1435.30

66

748.48
64

62
698.75
517.50
60

%T
58

56

54

52

50

48

46 835.76

43.9
4400.0 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

Figure S16: FTIR spectrum of 7.

73.9

73

72

71

70 3058.82 1432.04 1091.26

1599.44
69
2851.47
2063.62
68
3436.11 2923.90

67 749.97
515.87
66

697.32
%T 65

64

63

62

61

60

59

58
842.36

56.6
4400.0 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
cm-1

Figure S17: FTIR spectrum of 8.

20
 1.d HRMS Data

Figure S18. HRMS of 1.

Figure S19. HRMS of 2.

21
Figure S20. HRMS of 3.

Figure S21. HRMS of 4.

22
Figure S22. HRMS of 5.

Figure S23. HRMS of 6.

Figure S24. HRMS of 7.

Figure S25. HRMS of 8.

23
 1e. CHN analysis
Complex CHN data
5
Anal. Calc.:
C, 64.29;
H, 4.22;
N, 3.26.
Found:
C, 63.48;
H, 4.85;
N, 3.45.

6
Anal. Calc.
C, 64.52;
H, 4.33;
N, 3.22.
Found:
C, 64.03;
H, 4.39;
N, 3.37.
7
Anal. Calc.
C, 63.41;
H, 4.09;
N, 3.21.
Found:
C, 62.98;
H, 3.92;
N, 3.22.
8

Anal. Calc.
C, 64.02;
H, 4.46;
N, 4.21.
Found:
C, 63.76;
H, 4.47;
N, 4.19.

24
 2. Crystallographic data and refinement parameters

Table S1. Crystallographic data and refinement parameters for complex 3, 6 and 7.

Complex 3 Complex 6 Complex 7

Empirical formula C57 H44 Cl F7 N3 C70 H56 F6 Fe N3 C69 H53 F7 Fe N3
P3 Ru P3 Ru P3 Ru
Formula weight 1133.43 1303.00 1306.97
Crystal system Triclinic Triclinic Triclinic
Space group Pī Pī Pī
a, Å 10.5364(8) 10.584(2) 10.5529(14)
b, Å 14.7483(12) 17.667(4) 13.3570(18)
c, Å 16.2593(13) 34.718(7) 24.191(3)
, deg 93.488(2) 89.890(7) 103.923(6)
, deg 107.922(2) 89.872(7) 97.939(7)
, deg 90.630(2) 78.798(6) 91.568(7)
3
V, Å 2398.4(3) 6368(2) 3271.4(8)
Z 2 4 2
calcd, g cm -3 1.5694 1.359 1.327
, mm -1 0.555 0.601 0.587
F(000) 1150.9837 2664 1332
Collected 29734 73119 23767
independent 9643 22146 10642
Observed [I > 2(I)] 8245 9423 8246
No. of variables 649 1515 757
Goodness-of-fit 1.0405 0.928 1.037
a R1 = 0.0389 0.0827 0.0577
Final R indices [I>2(I)]
wR2 = 0.1006 0.1711 0.1528
R indices (all data)a R1 = 0.0471 0.1890 0.0755
wR2 = 0.1070 0.2210 0.1641
a
R1 = Fo – Fc/Fo with Fo >2(Fo ). wR2 = [w(Fo  – Fc ) /Fo  ]; The single crystal data
2 2 2 2 2 22

was collected at 100 K for the single crystals 3, 6 and 298 K for 7.

25
 2 4
3
Figure S25. ORTEP diagram of complex 2 and 4 with hydrogen atoms omitted for the sake of
clarity. The thermal ellipsoids are drawn at 40% of probability.

Note: The single crystals for complexes 2 and 4 were attempted. Multiple attempts were made to
grow better diffracting crystals. The diffraction data for the complexes 2 and 4 were poor in
quality. Moreover, data was collected at room temperature (298 K). Accordingly, the resultant
diffraction data reflects poor R values, which are quite higher (R = 16 and 14% respectively).
However, there is no ambiguity in modeling the atoms. Please see Table S2 for the
Crystallographic data and refinement parameters for complexes 2 and 4.

26
Table S2. Crystallographic data and refinement parameters for complexes 2 and 4.

Complex 2 Complex 4

Empirical formula C58 H47 Cl F6 N3 C59 H51 Cl F6 N4

P3 Ru P3 Ru
Formula weight 1129.47 1159.46
Crystal system Triclinic Monoclinic
Space group Pī P21/C
a, Å 10.662(7) 10.6724(6)
b, Å 15.274(10) 32.8404(17)
c, Å 17.471(12) 16.5648(10)
, deg 114.358(19) 90
, deg 101.21(2) 93.216(4)
, deg 90.29(2) 90
V, Å3 2531(3) 5796.6(6)
Z 2 5
calcd, g cm -3 1.5694 1.570
, mm -1 0.523 0.535
F(000) 1150.9543 2790
Collected 8504 53478
independent 3770 14266
Observed [I > 2(I)] 8504 5743
No. of variables 656 670
Goodness-of-fit 1.0954 1.042
a R = 0.1674 0.1412
Final R indices [I>2(I)] 1
wR2 = 0.3762 0.3257
a
R indices (all data) R1 = 0.2608 0.2965
wR2 = 0.4512 0.3926
a
R1 = Fo – Fc/Fo with Fo >2(Fo ). wR2 = [w(Fo  – Fc ) /Fo22]; The single crystal data
2 2 2 2 2

was collected at 298 K.

27
 3. Photophysical studies

Figure S26: Absorption spectra of (a) complexes 1-4 and (b) complexes 5-8 in 1×10-5 M DCM
solution at 28 °C.

Table S3. Absorption spectral data of complexes 1-8 at 28 °C.

Complexes Absorption (nm)a

λmax (ε×10-4 in M-1cm-1)
1 272 (9.01), 313 (6.18), 492 (1.12)
2 272 (9.65), 314 (6.63), 494 (1.22)
3 271 (9.82), 312 (6.72), 493 (1.23)
4 257 (9.91), 312 (2.32), 397 (0.81), 507 (0.67)
5 274 (6.06), 315 (3.68), 495 (0.51)
6 276 (6.31), 313 (3.79), 498 (0.72)
7 274 (6.86), 316 (4.39), 499 (1.07)
8 272 (6.66), 312 (4.44), 492 (1.37)
a
Absorption data recorded in 1×10-5 M in DCM; ε = Absorption coefficient

4. Electrochemical Characterization

Cyclic voltammetric analysis was conducted in DCM using n-Bu4NPF6 (0.1 M) as supporting
electrolytes, Pt wire counter electrode and Ag/AgCl reference electrode.

28
Figure S27: Cyclic voltammogram of DCM using TBAPF6 as supporting electrolyte (Blank
run), Pt disc working electrode. Scan rate at 100 mV/s.

Figure S28: Cyclic voltammogram of complex acetynyl ferrocene in DCM using [(n-Bu)4N]PF6
as supporting electrolyte, Pt disc working electrode, and Ag/AgCl reference electrode. Scan rate
at 100 mV/s.

Figure S29: Cyclic voltammogram of complex 1-4 in DCM using [(n-Bu)4N]PF6 as supporting
electrolyte, Pt disc working electrode, and Ag/AgCl reference electrode. Scan rate at 100 mV/s.

29
Figure S30: Cyclic voltammogram of complex 5-8 in DCM using [(n-Bu)4N]PF6 as supporting
electrolyte, Pt disc working electrode, and Ag/AgCl reference electrode. Scan rate at 100 mV/s.

5. Theoretical studies
The geometries of complexes were optimized using density functional theory with hybrid
CAM-B3LYP functional that takes care of long range interactions.4 The Fe and Ru metal centres
were described by the LANL2DZ basis set5, while the 6-31G** basis set 6 was employed for all
other atoms.

Table S4: Comparison of the experimental and computed bond distances. The experimental
bond distances are in the parentheses as obtained from solid state structures (SCXRD studies).

Bond Distance (Å) Complex 5 Complex 6 Complex 7 Complex 8

Ru1-N3 2.14 2.15(2.11) 2.14(2.10) 2.14

Ru1-N2 2.04 2.04(2.02) 2.04(2.01) 2.04
Ru1-N1 2.15 2.14(2.12) 2.14(2.10) 2.15
Ru1-P1 2.45 2.45(2.38) 2.44(2.37) 2.45
Ru1-P2 2.45 2.45(2.39) 2.45(2.38) 2.44
Ru1-Cacetylide 2.06 2.05(2.05) 2.05(2.06) 2.06
C≡C 1.22 1.22(1.14) 1.22(1.17) 1.22

30
 Figure S31. Computed electronic spectra for complexes 5 and 5+.

Table S5: Comparison of bond distances obtained from the optimized geometries of complexes
5 and 6 as well as their one-electron oxidized counterparts (5+ and 6+).

Bond Complex 6 Complex 6+ Complex 5 Complex 5+

Ru1-N3 2.15 2.15 2.14 2.15
Ru1-N2 2.04 2.05 2.04 2.05
Ru1-N1 2.14 2.14 2.15 2.16
Ru1-P1 2.45 2.44 2.45 2.46
Ru1-P2 2.45 2.45 2.45 2.46
Ru1-Cacetylide 2.05 2.00 2.06 2.03
C≡C 1.22 1.24 1.22 1.23
Fe-Cp(C≡C) 1.72 1.91 1.71 1.89
Fe-Cp 1.66 1.88 1.69 1.75

31
Table S6: Molecular orbital decomposition of the neutral complexes. Numbers are in %.

Fe orbital Cp orbital C≡C orbital Ru orbital 4'-(aryl)-

Contribution Contribution Contribution Contribution 2,2':6',2''-tpy
(d) (p) (p) (d) moiety orbital
contribution (p)
Complex 5
HOMO-1 44.77 5.1 22.7 15.4 0

HOMO 16.5 16.5 31.12 23.8 0

LUMO 0 0 0 3.85 87.6
LUMO+1 0 0 0 0.92 93.4
Complex 6
HOMO-1 12.8 3.8 35.7 30.9 0
HOMO 10.2 13.8 35.4 30.83 0
LUMO 0 0 0 3.74 87.9
LUMO+1 0 0 0 0.96 93.0
Complex 7
HOMO-1 46.3 5.0 21.9 14.7 0
HOMO 17.4 16.8 33.1 23.4 0
LUMO 0 0 0 3.80 87.6
LUMO+1 0 0 0 0.92 93.3
Complex 8
HOMO-1 9.3 0.65 16.8 20.28 27+13.8(terminal
amine group)
HOMO 15.2 16.2 33.1 25.0 0
LUMO 0 0 0 4.0 87.0
LUMO+1 0 0 0 0.95 93.35

32
 Table S7: Spin orbital decomposition (in %) for the one-electron oxidized complexes.
Fe orbital Cp orbital C≡C orbital Ru orbital 4'-(aryl)-2,2':6',2''-tpy
contribution (d) contribution (p) contribution (p) contribution (d) moiety orbital
contribution (p)
Complex 5+
α HOSO-1 0 0.63 23.7 51.1 10.64
β HOSO-1 0 1.10 23.8 51.8 10.58
α HOSO 3.8 9.87 23.01 49.25 0
β HOSO 3.7 8.0 24.3 49.7 1.39
α LUSO 35.6 49.5 7.26 1.68 0
β LUSO 67.2 21.26 5.14 1.15 0
α LUSO+1 44.9 52.9 0.10 0 0
β LUSO+1 0.83 0 0 2.53 87.08
Complex 6+
α HOSO-1 0 0 15.57 40.1 34.45
β HOSO-1 0 0.6 16.01 40.67 32.3
α HOSO 7.79 10.8 18.81 48.58 1.40
β HOSO 3.30 6.65 23.1 48.1 1.45
α LUSO 29.3 50.25 12.1 4.8 1.40
β LUSO 9.2 86.8 0 0 0
α LUSO+1 8.66 86.04 0 0 0
β LUSO+1 69.07 21.06 4.1 1.01 0
+
Complex 7
α HOSO-1 0 1.6 22.42 50.0 15.0
β HOSO-1 0 1.5 21.86 49.9 15.1
α HOSO 3.8 9.83 23.2 48.45 1.25
β HOSO 3.5 8.39 23.9 48.92 1.31
α LUSO 35.93 49.36 6.30 1.65 0
β LUSO 67.26 22.02 5.13 1.14 1.31
α LUSO+1 44.93 53.01 0 0 0
β LUSO+1 0.88 0 0 2.55 86.5
Complex 8+
α HOSO-1 3.37 9.88 25.8 49.27 1.5
β HOSO-1 3.5 8.5 29.2 50.4 1.6
α HOSO 0 0 0.50 4.86 82 (30.5 terminal amine
group)
β HOSO 0 0 0 4.8 82.5 (30.6 terminal amine
group)
α LUSO 35.7 49.9 7.3 1.82 0
β LUSO 67.03 22.01 5.29 1.20 0
α LUSO+1 44.6 52.85 0 0 0
β LUSO+1 0 0 0 3.1 87.00

33
Figure S32. Electronic transitions corresponding to the computed NIR band centred at 1127 nm.

Table S8: Fe and Ru d-orbital contribution (in %) in the frontier spin orbitals of complex 5+.

Complex 5+ Ru d-orbital contribution Fe d-orbital contribution

(%) (%)
HOSO-26β 3.42 10.00
HOSO-25β 0.68 63.6
HOSO-24β 0.80 26.7
HOSO 49.3 4.50
LUSO 1.15 67.2

Table S9: NIR band obtained from TDDFT calculation for the mono-oxidized complex 5+.

λ/nm Exp. Value Oscillator Major contributions Assignment

(Theoretical) (nm) strength (f) (Relative contribution in %)
1127.67 (1.1) 1403 0.0017 HOSO-26β -> LUSO (53) Charge transfer
HOSO-25β -> LUSO (18) from Metal (Ru) to
HOSO-24β -> LUSO (9) Metal (Fe)
(MM'CT)

34
6. References
1. Kröhnke, F. The specific synthesis of pyridines and oligopyridines. Synthesis 1976, 1, 1.
2. Rosenblum, M.; Brawn, N.; Papenmeier, J.; Applebaum, M. Synthesis of
ferrocenylacetylenes. J. Organometal. Chem. 1966, 6, 173.
3. Farrugia, L. J. ORTEP-3 for windows - A Version of ORTEP-III with a Graphical User
Interface (GUI). J. Appl. Cryst. 1997, 30, 565.
4. Yanai, T.; Tew, D. P.; Handy, N.C. A new hybrid exchange-correlation functional using
the Coulomb-attenuating method (CAM-B3LYP), Chem. Phys. Lett., 2004, 393, 51-57.
5. (a) Hay, P. J.; Wadt, W. R. Ab initio effective core potentials for molecular calculations.
potentials for the transition metal atoms Sc to Hg, J. Chem. Phys., 1985, 82, 270-283. (b)
Hay, P. J.; Wadt, W. R. Ab initio Effective Core Potentials for Molecular Calculations.
Potentials for Main Group Elements Na to Bi, J. Chem. Phys., 1985, 82, 284-298. (c)
Hay, P. J. and Wadt, W. R. Ab initio Effective Core Potentials for Molecular
Calculations. Potentials for K to Au Including the Outermost Core Orbitals, J. Chem.
Phys., 1985, 82, 299-310.
6. Hariharan, P. C. and Pople, J. A. Influence of polarization functions on molecular-orbital
hydrogenation energies, Theor. Chem. Acc., 1973, 28, 213-225.

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