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
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