Tables and Supporting information
SUPPORTING INFORMATION:
Table captions:
Table S1.Energy of the frontier molecular orbitals in eV for dyes5aand 5b.
Table S2. Energy of the frontier molecular orbitals in eV for dyes6aand 6b.
Table S3. Onsager radii of the dyes 5a, 5b, 6a and 6b at the ground and excited states in various solvents using DFT computations at B3LYP/6-31G(d) level. (radius in Å)
Table S4.Static first hyperpolarizability and its β-components of dyes 5a, 5b, 6a and 6b.(all values are given in e.s.u.)
Table S1.Energy of the frontier molecular orbitals in eV for dyes5aand 5b.
Dye / Orbital no. / FMO / 1,4-Dioxane / Toluene / DCM / Acetone / DMF5a / 102 / L+3 / -0.396 / -0.397 / -0.417 / -0.427 / -0.431
101 / L+2 / -0.752 / -0.752 / -0.753 / -0.755 / -0.756
100 / L+1 / -1.120 / -1.116 / -1.071 / -1.062 / -1.058
99 / LUMO / -2.631 / -2.635 / -2.685 / -2.698 / -2.702
98 / HOMO / -5.609 / -5.607 / -5.585 / -5.580 / -5.579
97 / H-1 / -6.145 / -6.142 / -6.111 / -6.111 / -6.104
96 / H-2 / -6.607 / -6.608 / -6.614 / -6.617 / -6.618
95 / H-3 / -7.055 / -7.054 / -7.049 / -7.049 / -7.050
HOMO-LUMO / 2.977 / 2.971 / 2.899 / 2.882 / 2.876
5b / 115 / L+3 / -0.177 / -0.183 / -0.258 / -0.280 / -0.288
114 / L+2 / -0.474 / -0.478 / -0.547 / -0.567 / -0.574
113 / L+1 / -1.003 / -1.003 / -1.011 / -1.014 / -1.016
112 / LUMO / -2.397 / -2.405 / -2.508 / -2.535 / -2.545
111 / HOMO / -5.453 / -5.456 / -5.488 / -5.498 / -5.501
110 / H-1 / -6.022 / -6.023 / -6.042 / -6.049 / -6.052
109 / H-2 / -6.473 / -6.477 / -6.536 / -6.551 / -6.557
108 / H-3 / -6.854 / -6.859 / -6.927 / -6.946 / -6.954
HOMO-LUMO / 3.056 / 3.050 / 2.980 / 2.962 / 2.956
Table S2. Energy of the frontier molecular orbitals in eV for dyes6aand 6b.
Dye / Orbital no. / FMO / 1,4-Dioxane / Toluene / DCM / Acetone / DMF6a / 148 / L+3 / -0.987 / -0.980 / -0.905 / -0.887 / -0.880
147 / L+2 / -1.453 / -1.441 / -1.301 / -1.266 / -1.252
146 / L+1 / -2.697 / -2.694 / -2.662 / -2.653 / -2.650
145 / LUMO / -2.925 / -2.923 / -2.898 / -2.891 / -2.888
144 / HOMO / -5.819 / -5.811 / -5.716 / -5.692 / -5.683
143 / H-1 / -6.218 / -6.211 / -6.131 / -6.110 / -6.102
142 / H-2 / -6.825 / -6.817 / -6.733 / -6.711 / -6.703
141 / H-3 / -6.959 / -6.955 / -6.905 / -6.893 / -6.888
HOMO-LUMO / 2.894 / 2.889 / 2.819 / 2.801 / 2.794
6b / 174 / L+3 / -0.738 / -0.737 / -0.719 / -0.709 / -0.677
173 / L+2 / -1.351 / -1.343 / -1.232 / -1.200 / -1.188
172 / L+1 / -2.449 / -2.450 / -2.469 / -2.473 / -2.474
171 / LUMO / -2.673 / -2.675 / -2.699 / -2.705 / -2.707
170 / HOMO / -5.655 / -5.651 / -5.593 / -5.576 / -5.569
169 / H-1 / -6.055 / -6.052 / -6.011 / -5.997 / -5.992
168 / H-2 / -6.683 / -6.680 / -6.637 / -6.625 / -6.620
167 / H-3 / -6.794 / -6.795 / -6.809 / -6.86 / -6.819
HOMO-LUMO / 2.983 / 2.976 / 2.894 / 2.871 / 2.862
Table S3. Onsager radii of the dyes 5a, 5b, 6a and 6b at the ground and excited states in various solvents using DFT computations at B3LYP/6-31G(d) level. (radius in Å)
Solvent / Onsager radius (a0)5a / 5b / 6a / 6b
GS[a] / ES[b] / GS / ES / GS / ES / GS / ES
Toluene / 5.95 / 5.96 / 5.86 / 5.83 / 6.74 / 6.91 / 6.77 / 6.64
1,4-Dioxane / 5.69 / 5.78 / 6.05 / 6.05 / 6.41 / 6.36 / 6.75 / 7.04
DCM / 5.84 / 6.18 / 6.03 / 6.09 / 6.47 / 6.42 / 7.11 / 6.83
Ethyl acetate / 5.65 / 6.00 / 5.88 / 5.93 / 6.72 / 6.64 / 6.76 / 6.65
Acetone / 5.57 / 5.80 / 6.22 / 5.85 / 6.35 / 6.25 / 6.91 / 6.84
Methanol / 5.84 / 5.73 / 5.64 / 5.97 / 6.29 / 6.73 / 6.94 / 6.87
Acetonitrile / 5.95 / 5.69 / 5.96 / 6.23 / 6.61 / 6.12 / 6.83 / 6.89
DMF / 6.10 / 5.95 / 5.88 / 6.20 / 6.45 / 6.27 / 6.94 / 6.63
[a]GS = Ground state; [b]ES = Excited state.
Table S4.Static first hyperpolarizability and its β-components of dyes 5a, 5b, 6a and 6b.(all values are given in e.s.u.)
β-tensors / 5a / 5b / 6a / 6bβxxx / 1.31×10-28 / 1.20×10-28 / -4.53×10-34 / 6.39×10-33
βxxy / -3.67×10-30 / 1.97×10-29 / -1.08×10-28 / 8.71×10-29
βxyy / -6.77×10-30 / -7.21×10-31 / 1.97×10-34 / -3.37×10-34
βyyy / -7.31×10-31 / -4.83×10-30 / -1.01×10-29 / 8.26×10-30
βxxz / 9.54×10-31 / 6.11×10-31 / -6.03×10-30 / -1.12×10-29
βyyz / 2.34×10-31 / 1.79×10-31 / -4.75×10-31 / -2.80×10-30
βxzz / -2.57×10-32 / 1.07×10-31 / -2.25×10-36 / 4.40×10-35
βyzz / 2.12×10-31 / 6.67×10-32 / -4.75×10-31 / 1.80×10-31
βzzz / -8.42×10-32 / -5.23×10-32 / 2.42×10-31 / 4.90×10-32
o / 124.44×10-30 / 120.52×10-30 / 119.21×10-30 / 96.54×10-30
Figure captions:
Figure S1. Optimized geometry of dye 5b in DMF solvent in the ground and excited states(bond lengths are in Å, dihedral angles are in).
Figure S2. Optimized geometry of dye 6a in DMF solvent in the ground and excited states(bond lengths are in Å, dihedral angles are in ).
Figure S3. Optimized geometry of 6b in DMF solvent in the ground and excited states(bond lengths are in Å, dihedral angles are in).
Figure S4.Mulliken charges for dye 5a in DMF at ground and excited state optimized geometries.
Figure S5.Mulliken charges for dye 5b in DMF at ground and excited states optimized geometries.
Figure S6.Mulliken charges for dye 6a in DMF at ground and excited states optimized geometries.
Figure S7.Mulliken charges for dye 6b in DMF at ground and excited states optimized geometries.
Figure S8. Absorption spectra of dye 5bin different solvents.
Figure S9.Absorption spectra of dye6a in different solvents.
Figure S10.Absorption spectra of dye 6b in different solvents.
Figure S11.Plot of experimental emission maxima versus emission calculated from excited state optimization for dye 5b.
Figure S12.Plot of experimental emission maxima versus emission calculated from excited state optimization for dye 6a.
Figure S13. Plot of experimental emission maxima versus emission calculated from excited state optimization for dye 6b.
Figure S14. Electronic transitions for dye 5a.
Figure S15. Electronic transitions for dye 6a.
Figure S16. Electronic transitions for dye 6b.
Figure S1. Optimized geometry of dye 5b in DMF solvent in the ground and excited states(bond lengths are in Å, dihedral angles are in).
Figure S2. Optimized geometry of dye 6a in DMF solvent in the ground and excited states(bond lengths are in Å, dihedral angles are in ).
Figure S3. Optimized geometry of 6b in DMF solvent in the ground and excited states (bond lengths are in Å, dihedral angles are in).
Figure S4.Mulliken charges for dye 5a in DMF at ground and excited state optimized geometries.
Figure S5.Mulliken charges for dye 5b in DMF at ground and excited states optimized geometries.
Figure S6.Mulliken charges for dye 6a in DMF at ground and excited state optimized geometries.
Figure S7.Mulliken charges for dye 6b in DMF at ground and excited state optimized geometries.
Figure S8. Absorption spectra of dye 5bin different solvents.
*a.u.: arbitrary unit
Figure S9.Absorption spectra of dye6a in different solvents.
*a.u.: arbitrary unit
Figure S10.Absorption spectra of dye 6b in different solvents.
*a.u.: arbitrary unit
Figure S11.Plot of experimental emission maxima versus emission calculated from excited state optimization for dye 5b.
Figure S12.Plot of experimental emission maxima versus emission calculated from excited state optimization for dye 6a.
Figure S13. Plot of experimental emission maxima versus emission calculated from excited state optimization for dye 6b.
Figure S14. Electronic transitions for dye 5a.
*a.u.: arbitrary unit
Figure S15. Electronic transitions for dye 6a.
*a.u.: arbitrary unit
Figure S16. Electronic transitions for dye 6b.
*a.u.: arbitrary unit
Cartesian coordinate captions:
Cartesian coordinates 1. Optimized geometry for dye 5ain DMF [B3LYP/6-31G(d)].
Cartesian coordinates 2. Optimized geometry for dye 5b in DMF[B3LYP/6-31G(d)].
Cartesian coordinates 3. Optimized geometry for dye 6a in DMF[B3LYP/6-31G(d)].
Cartesian coordinates 4. Optimized geometry for dye 6b in DMF[B3LYP/6-31G(d)].
Cartesian coordinates 1. Optimized geometry for dye 5ain DMF [B3LYP/6-31G(d)].
C 3.05837600 1.31419300 0.13590800
C 3.42420600 2.68459000 0.25324500
C 2.48030300 3.69328100 0.34031200
C 1.12463400 3.33148800 0.31321900
C 0.72490300 1.97137900 0.19572200
C 1.69035200 0.97445800 0.11006700
H 4.47336400 2.95923300 0.27613200
H 2.79126800 4.72903300 0.42424100
H 1.39848000 -0.06860900 0.02071300
C -1.12463400 3.33148800 0.31321900
C -2.48030300 3.69328100 0.34031200
C -3.42420600 2.68459000 0.25324500
C -3.05837600 1.31419300 0.13590800
C -1.69035200 0.97445800 0.11006700
C -0.72490300 1.97137900 0.19572200
H -2.79126800 4.72903300 0.42424100
H -4.47336400 2.95923300 0.27613200
H -1.39848000 -0.06860900 0.02071300
N 0.00000000 4.13408600 0.39343900
C 0.00000000 5.59656200 0.46895200
C 0.00000000 6.26718900 -0.90678500
H 0.87694400 5.89628900 1.04898400
H -0.87694400 5.89628900 1.04898400
H 0.00000000 7.35533600 -0.78528000
H 0.88774100 5.98549200 -1.48200100
H -0.88774100 5.98549200 -1.48200100
C 4.02747300 0.24244100 0.03894300
C 5.38733100 0.35775700 0.01293600
H 3.60008900 -0.75486300 -0.02997500
H 5.84138900 1.34388800 0.04026500
C 6.29067700 -0.75421300 -0.09635000
C 7.64863200 -0.53202700 -0.31213700
C -4.02747300 0.24244100 0.03894300
C -5.38733100 0.35775700 0.01293600
H -3.60008900 -0.75486300 -0.02997500
H -5.84138900 1.34388800 0.04026500
C -6.29067700 -0.75421300 -0.09635000
C -7.64863200 -0.53202700 -0.31213700
C -5.79696500 -2.15265000 0.02296000
C -5.11597400 -2.57008700 1.17956700
C -6.00998800 -3.07435200 -1.01548500
C -4.66872700 -3.88571100 1.29663600
H -4.95668900 -1.86778800 1.99195500
C -5.54624500 -4.38437000 -0.90055100
H -6.51982900 -2.75778300 -1.92032000
C -4.87913500 -4.79408300 0.25633900
H -4.15532800 -4.19969700 2.20075500
H -5.70597400 -5.08383900 -1.71589600
H -4.52380500 -5.81658800 0.34643100
C 5.79696500 -2.15265000 0.02296000
C 6.00998800 -3.07435200 -1.01548500
C 5.11597400 -2.57008700 1.17956700
C 5.54624500 -4.38437000 -0.90055200
H 6.51982900 -2.75778300 -1.92032000
C 4.66872700 -3.88571100 1.29663600
H 4.95668900 -1.86778800 1.99195500
C 4.87913500 -4.79408300 0.25633900
H 5.70597400 -5.08383900 -1.71589600
H 4.15532700 -4.19969700 2.20075500
H 4.52380500 -5.81658800 0.34643100
C 8.17960900 0.77914700 -0.50727600
N 8.62165700 1.84574700 -0.66790900
C 8.61877800 -1.57835800 -0.31834800
N 9.45133800 -2.39435900 -0.31872200
C -8.17960900 0.77914700 -0.50727600
N -8.62165700 1.84574700 -0.66790900
C -8.61877800 -1.57835800 -0.31834800
N -9.45133800 -2.39435900 -0.31872200
Cartesian coordinates 2. Optimized geometry for dye 5b in DMF[B3LYP/6-31G(d)].
C -5.57767500 -0.21363700 -0.08426400
C -6.95723900 0.00404400 -0.01598500
C -7.39481900 1.30393000 0.23505200
C -6.48643200 2.36250700 0.41663400
C -5.11277100 2.13971500 0.35092400
C -4.64770800 0.84319600 0.10045100
C -3.32990600 0.25488800 -0.03121700
C -2.03591900 0.76001800 0.04127900
C -0.92880900 -0.09538600 -0.13448600
C -1.16416100 -1.47657800 -0.38878300
C -2.44151300 -2.00313700 -0.46661000
C -3.53045900 -1.13242100 -0.28980900
N -4.88217000 -1.39841700 -0.33142000
H -7.66980500 -0.80367100 -0.14881200
H -8.46183600 1.49983300 0.29316500
H -6.86186700 3.36285800 0.61145700
H -4.41329200 2.95916100 0.49306900
H -1.86805800 1.81641300 0.23573500
H -0.32085700 -2.14479500 -0.52814600
H -2.58701300 -3.06130500 -0.65742300
C -5.49236300 -2.71273200 -0.52059600
C -5.74605800 -3.45581700 0.79403900
H -4.83447300 -3.29377100 -1.17286600
H -6.42747000 -2.56730300 -1.06954000
H -6.20949100 -4.42644800 0.58790500
H -4.80931100 -3.62961100 1.33341800
H -6.41737900 -2.88586800 1.44435400
C 0.39831900 0.47713400 -0.04838800
C 1.58856400 -0.18662400 -0.14981300
C 2.87049000 0.45925300 -0.06146200
C 4.07139400 -0.24318800 0.00006000
C 5.30895400 0.47060500 -0.04890200
N 6.32740200 1.03607900 -0.10345900
H 0.41956500 1.55017600 0.12682000
H 1.60307800 -1.26112900 -0.26931700
C 2.92566400 1.95435300 -0.05012600
C 3.40512900 2.64013400 1.07691200
C 3.44994400 4.03433500 1.08896800
C 3.03063900 4.75995900 -0.02869500
C 2.55644300 4.08535700 -1.15621200
C 2.49491800 2.69146200 -1.16494900
H 2.12388000 2.16945600 -2.04203300
H 2.23130700 4.64302300 -2.02993500
H 3.07162800 5.84551600 -0.02037800
H 3.81333700 4.55266000 1.97178500
H 3.73106800 2.07907500 1.94792600
C 4.18727100 -1.72256000 0.08579000
O 3.26363300 -2.51905500 0.15860600
O 5.48031300 -2.10594700 0.08080000
C 5.73214200 -3.53151300 0.16820700
C 7.23515700 -3.72924200 0.14592200
H 5.24025700 -4.02481400 -0.67548300
H 5.28165700 -3.90920900 1.09102400
H 7.46327500 -4.79818600 0.21180500
H 7.66830500 -3.34117000 -0.78146400
H 7.71012300 -3.22282500 0.99220400
Cartesian coordinates 3. Optimized geometry for dye 6a in DMF[B3LYP/6-31G(d)].
C 3.05837600 1.31419300 0.13590800
C 3.42420600 2.68459000 0.25324500
C 2.48030300 3.69328100 0.34031200
C 1.12463400 3.33148800 0.31321900
C 0.72490300 1.97137900 0.19572200
C 1.69035200 0.97445800 0.11006700
H 4.47336400 2.95923300 0.27613200
H 2.79126800 4.72903300 0.42424100
H 1.39848000 -0.06860900 0.02071300
C -1.12463400 3.33148800 0.31321900
C -2.48030300 3.69328100 0.34031200
C -3.42420600 2.68459000 0.25324500
C -3.05837600 1.31419300 0.13590800
C -1.69035200 0.97445800 0.11006700
C -0.72490300 1.97137900 0.19572200
H -2.79126800 4.72903300 0.42424100
H -4.47336400 2.95923300 0.27613200
H -1.39848000 -0.06860900 0.02071300
N 0.00000000 4.13408600 0.39343900
C 0.00000000 5.59656200 0.46895200
C 0.00000000 6.26718900 -0.90678500
H 0.87694400 5.89628900 1.04898400
H -0.87694400 5.89628900 1.04898400
H 0.00000000 7.35533600 -0.78528000
H 0.88774100 5.98549200 -1.48200100
H -0.88774100 5.98549200 -1.48200100
C 4.02747300 0.24244100 0.03894300
C 5.38733100 0.35775700 0.01293600
H 3.60008900 -0.75486300 -0.02997500
H 5.84138900 1.34388800 0.04026500
C 6.29067700 -0.75421300 -0.09635000
C 7.64863200 -0.53202700 -0.31213700
C -4.02747300 0.24244100 0.03894300
C -5.38733100 0.35775700 0.01293600
H -3.60008900 -0.75486300 -0.02997500
H -5.84138900 1.34388800 0.04026500
C -6.29067700 -0.75421300 -0.09635000
C -7.64863200 -0.53202700 -0.31213700
C -5.79696500 -2.15265000 0.02296000
C -5.11597400 -2.57008700 1.17956700
C -6.00998800 -3.07435200 -1.01548500
C -4.66872700 -3.88571100 1.29663600
H -4.95668900 -1.86778800 1.99195500
C -5.54624500 -4.38437000 -0.90055100
H -6.51982900 -2.75778300 -1.92032000
C -4.87913500 -4.79408300 0.25633900
H -4.15532800 -4.19969700 2.20075500
H -5.70597400 -5.08383900 -1.71589600
H -4.52380500 -5.81658800 0.34643100
C 5.79696500 -2.15265000 0.02296000
C 6.00998800 -3.07435200 -1.01548500
C 5.11597400 -2.57008700 1.17956700
C 5.54624500 -4.38437000 -0.90055200
H 6.51982900 -2.75778300 -1.92032000
C 4.66872700 -3.88571100 1.29663600
H 4.95668900 -1.86778800 1.99195500
C 4.87913500 -4.79408300 0.25633900
H 5.70597400 -5.08383900 -1.71589600
H 4.15532700 -4.19969700 2.20075500
H 4.52380500 -5.81658800 0.34643100
C 8.17960900 0.77914700 -0.50727600
N 8.62165700 1.84574700 -0.66790900
C 8.61877800 -1.57835800 -0.31834800
N 9.45133800 -2.39435900 -0.31872200
C -8.17960900 0.77914700 -0.50727600
N -8.62165700 1.84574700 -0.66790900
C -8.61877800 -1.57835800 -0.31834800
N -9.45133800 -2.39435900 -0.31872200
Cartesian coordinates 4. Optimized geometry for dye 6b in DMF[B3LYP/6-31G(d)].
C -3.05873300 -0.96274600 0.22879300
C -3.42426800 -2.32656800 0.40384200
C -2.48068000 -3.33182500 0.53368400
C -1.12489900 -2.97309100 0.49174300
C -0.72486700 -1.61970800 0.31584300
C -1.69112200 -0.62650700 0.18826900
C 1.12489700 -2.97309100 0.49175300
C 2.48067800 -3.33182500 0.53370500
C 3.42426700 -2.32656800 0.40387100
C 3.05873400 -0.96274600 0.22882000
C 1.69112200 -0.62650600 0.18828500
C 0.72486700 -1.61970800 0.31584900
N -0.00000100 -3.77219500 0.60718200
C -0.00000200 -5.22832400 0.75483900
C 0.00000600 -5.96932300 -0.58455900
C -4.03045600 0.10597800 0.08847900
C -5.38877900 -0.01786900 0.06622200
C -6.28920600 1.10016300 -0.06759200
C -7.65687800 0.97319200 -0.28112700
C 4.03045800 0.10597900 0.08851400
C 5.38878000 -0.01787200 0.06624600
C 6.28921000 1.10016100 -0.06755600
C 7.65687800 0.97318400 -0.28111600
C 5.72774900 2.48144300 0.06281100
C 5.15366600 2.90666200 1.27175500
C 5.76333300 3.36783600 -1.02505300
C 4.64016300 4.19815200 1.39294400
C 5.23237600 4.65229800 -0.90626100
C 4.67497400 5.07230400 0.30385000
C -5.72773400 2.48144700 0.06273000
C -5.76331000 3.36780400 -1.02516300
C -5.15364900 2.90670000 1.27166100
C -5.23234400 4.65226600 -0.90641300
C -4.64013700 4.19819100 1.39280800
C -4.67494100 5.07230700 0.30368500
C -8.48789000 2.13805400 -0.21556500
N -9.18632100 3.06897200 -0.15243900
C 8.48790400 2.13803400 -0.21552800
N 9.18635000 3.06894100 -0.15238200
C -8.46390000 -0.25164500 -0.54383900
O -9.68548900 -0.23268000 -0.54881500
O -7.73831100 -1.35291400 -0.80753700
C -8.47283700 -2.58083200 -1.07472100
C -8.82603200 -3.30691900 0.21297500
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