The effect of N-ligands on the geometry, bonding, and electronic

absorption properties of ruthenium carbonyl chainsSupplementary data

Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is (c) The Owner Societies 2010

3.2. Torsional Behaviour of the Ligands

Weak OH-O interactions in[Ru(phen(OH)2(CO)2]8H2

(distance ~4.1 – 4.2 Å)

While the effect is small in this case, perhaps morefar reaching substituentwould make the effectstronger

3.6. TD-DFT Calculations

• Spectra for studied dimeric complexes using~135 degree dihedral angles

• Sample spectra for dimeric complexes (bim, bpy ligands) using ~45 degree dihedral angles

• Sample spectra for n=4 chains (bim, bpyligands) using ~135 degree dihedral angles

• Summaries of similar low-energy excitations in n=2 and n=4 case

Key to Reading Excitations

HOMO LUMO

90%

68% Ru 91% bim

Amount of shownexcitation in composition

Compositions of orbitals

[Ru(bim)(CO)2]2H2, ~135 dihedral angle

L+6 HOMO

L+4

LUMO

90%

68% Ru 91% bim

83% Ru11% CO

51% Ru41% CO

53%

70%

[Ru(bpy)(CO)2]2H2, ~135 dihedral angle

HOMO LUMO

82%

L+2L+3

95% 93%

60% Ru 90% bpy

90% bpy89% bpy

[Ru(bpy(COOH)2)(CO)2]2H2, ~135 dihedral angle

HOMO

LUMO

75%

76%

L+1

49% Ru37% bpy

88% bpy

59% bpy

[Ru(bpy(OH)2)(CO)2]2H2, ~135 dihedral angle

HOMOLUMO

86%

L+1

92%

62% Ru94% bpy

72% bpy

[Ru(bpy(t-but)2)(CO)2]2H2, ~135 dihedral angle

HOMOLUMO

84%

L+3L+2

95%91%60% Ru

91% bpy

90% bpy88% bpy

[Ru(CO)4]2H2, ~135 dihedral angle

HOMO LUMO

83%

65% Ru30% CO

70% Ru30% CO

[Ru(phen)(CO)2]2H2, ~135 dihedral angle

HOMO LUMO

83%

60% Ru 90% phen

[Ru(phen(O)2)(CO)2]2H2, ~135 dihedral angle

HOMO L+2

82%

52% Ru 90% phen

[Ru(phen(OH)2)(CO)2]2H2, ~135 dihedral angle

HOMO LUMO

82%

59% Ru 90% phen

[Ru(terpy)(CO)]2H2, ~135 dihedral angle

HOMO

LUMO

89%

L+274% 36% Ru57% terpy

85% terpy

95% terpy

[Ru(bim)(CO)2]2H2, ~45 dihedral angle

L+4

HOMO

L+1

LUMO

90%

91% bim

37% Ru55% CO

67% Ru

89%

45%

63%

L+5

70% bim

89% Ru

TD spectrum

Wavelength, nm760740720700680660640620600580560540520500480460440420400380360340320300280260240220200

f

0.360.350.340.330.320.31

0.30.290.280.270.260.250.240.230.220.21

0.20.190.180.170.160.150.140.130.120.11

0.10.090.080.070.060.050.040.030.020.01

0

[Ru(bpy)(CO)2]2H2, ~45 dihedral angle

HOMO LUMO

84%

L+1L+2

83%

93%57% Ru

95% bpy

92% bpy

62% bpy

L+3

83%

84% bpy

TD spectrum

Wavelength, nm800750700650600550500450400350

f

0.54

0.52

0.5

0.48

0.46

0.44

0.42

0.4

0.38

0.36

0.34

0.32

0.3

0.28

0.26

0.24

0.22

0.2

0.18

0.16

0.14

0.12

0.1

0.08

0.06

0.04

0.02

0

[Ru(bpy)(CO)]4H2, ~135 dihedral angle

HOMO

LUMO87%

L+2

88%54% Ru32% bim

86% bim

85% Ru

L+1

L+6

86%

83%

71% bim25% Ru

90% bim

8% CO

TD spectrum

Wavelength, nm1 000950900850800750700650600550500450400350

f

0.31

0.3

0.29

0.280.27

0.26

0.25

0.240.23

0.22

0.210.2

0.19

0.18

0.170.16

0.15

0.14

0.130.12

0.11

0.10.09

0.08

0.07

0.060.05

0.04

0.03

0.020.01

0

[Ru(bim)(CO)]4H2, ~135 dihedral angle

HOMO L+1

87%

L+2

88%

37% Ru

LUMO

86%83% 75% bpy

51% bpyH-1LUMO

87% bpy

82% bpy

75% bpy78% Ru

Similar Low-Energy Excitationsn=2, Diherdal angle = ~135Complex Excitation % in composition λ (nm)

[Ru(bim)(CO)2]nH2 HOMO –> LUMO 90 544

[Ru(bpy)(CO)2]nH2 HOMO –> LUMO 82 732

[Ru(bpy(COOH)2)(CO)2]nH2 HOMO –> LUMO 75 824

[Ru(bpy(OH)2)(CO)2]nH2 HOMO –> LUMO 86 758

[Ru(bpy(t-but)2)(CO)2]nH2 HOMO –> LUMO 84 733

[Ru(phen)(CO)2]nH2 HOMO –> LUMO 83 733

[Ru(phen(O)2)(CO)2]nH2 HOMO –> LUMO+2 82 718

[Ru(phen(OH)2)(CO)2]nH2 HOMO –> LUMO 82 745

[Ru(terpy)(CO)2]nH2 HOMO –> LUMO 74 786

Similar Low-Energy Excitationsn=4, Diherdal angle = ~135Complex Excitation % in composition λ (nm)

[Ru(bim)(CO)2]nH2 HOMO –> LUMO+2 86 673

[Ru(bpy)(CO)2]nH2 HOMO –> LUMO+2 78 820

[Ru(bpy(COOH)2)(CO)2]nH2 HOMO –> LUMO+2 65 880

[Ru(bpy(OH)2)(CO)2]nH2 HOMO –> LUMO+2 79 929

[Ru(bpy(t-but)2)(CO)2]nH2 HOMO –> LUMO+2 80 840

[Ru(phen)(CO)2]nH2 HOMO –> LUMO+4 74 827

[Ru(phen(O)2)(CO)2]nH2 HOMO –> LUMO+6 80 800

[Ru(phen(OH)2)(CO)2]nH2 HOMO –> LUMO+2 51 831

[Ru(terpy)(CO)2]nH2 HOMO –> LUMO+4 65 930