20
SUPPORTING INFORMATION PM 10 8 6 4 2 0 Fig. S1. 1 H NMR (400MHz, (CD 3 ) 2 SO) of (MPI-1)-V-TCF
SUPPORTING INFORMATION
PPM 10 8 6 4 2 0
SpinWorks 4: faz
file: ...ды исследования\ЯМР\ЯМР_ДП\165\fid expt: <zg30>transmitter freq.: 400.132401 MHztime domain size: 20378 pointswidth: 5597.01 Hz = 13.9879 ppm = 0.274660 Hz/ptnumber of scans: 16
freq. of 0 ppm: 400.130001 MHzprocessed size: 65536 complex pointsLB: 0.100 GF: 0.0000
Fig. S1. 1H NMR (400MHz, (CD3)2SO) of (MPI-1)-V-TCF
PPM 8.8 8.4 8.0 7.6 7.2 6.8 6.4 6.0 5.6
SpinWorks 4: faz
file: ...ды исследования\ЯМР\ЯМР_ДП\165\fid expt: <zg30>transmitter freq.: 400.132401 MHztime domain size: 20378 pointswidth: 5597.01 Hz = 13.9879 ppm = 0.274660 Hz/ptnumber of scans: 16
freq. of 0 ppm: 400.130001 MHzprocessed size: 65536 complex pointsLB: 0.100 GF: 0.0000
Fig. S2. 1H NMR (5.5-9.0 ppm, 400 MHz, (CD3)2SO) of (MPI-1)-V-TCF
PPM 10 8 6 4 2 0
SpinWorks 4: no title
file: ...оды исследования\ЯМР\ЯМР_ДП\67\fid expt: <zg30>transmitter freq.: 600.133301 MHztime domain size: 33554 pointswidth: 7788.16 Hz = 12.9774 ppm = 0.232108 Hz/ptnumber of scans: 4
freq. of 0 ppm: 600.129999 MHzprocessed size: 8192 complex pointsLB: 0.100 GF: 0.0000
Fig. S3. 1H NMR (400MHz, CDCl3) of (MPI-1)-V-TCF
PPM 8.8 8.4 8.0 7.6 7.2 6.8 6.4 6.0 5.6
SpinWorks 4: no title
file: ...оды исследования\ЯМР\ЯМР_ДП\67\fid expt: <zg30>transmitter freq.: 600.133301 MHztime domain size: 33554 pointswidth: 7788.16 Hz = 12.9774 ppm = 0.232108 Hz/ptnumber of scans: 4
freq. of 0 ppm: 600.130010 MHzprocessed size: 8192 complex pointsLB: 0.100 GF: 0.0000
Fig. S4. 1H NMR (5.5-9.0 ppm, 400MHz, CDCl3) of (MPI-1)-V-TCF
PPM 160 120 80 40
SpinWorks 4: no title
file: ...оды исследования\ЯМР\ЯМР_ДП\68\fid expt: <zgdc30>transmitter freq.: 150.918309 MHztime domain size: 50720 pointswidth: 36231.88 Hz = 240.0761 ppm = 0.714351 Hz/ptnumber of scans: 4096
freq. of 0 ppm: 150.902805 MHzprocessed size: 131072 complex pointsLB: 3.000 GF: 0.0000
Fig. S5. 13C NMR (150MHz, CDCl3) of (MPI-1)-V-TCF
PPM 10 8 6 4 2 0
SpinWorks 4: faz
file: ...ды исследования\ЯМР\ЯМР_ДП\142\fid expt: <zg30>transmitter freq.: 400.132401 MHztime domain size: 20378 pointswidth: 5597.01 Hz = 13.9879 ppm = 0.274660 Hz/ptnumber of scans: 4
freq. of 0 ppm: 400.130001 MHzprocessed size: 65536 complex pointsLB: 0.100 GF: 0.0000
Fig. S6. 1H NMR (400MHz, (CD3)2SO) of (MPI-3)-V-TCF
PPM 8.8 8.4 8.0 7.6 7.2 6.8 6.4 6.0 5.6
SpinWorks 4: faz
file: ...ды исследования\ЯМР\ЯМР_ДП\142\fid expt: <zg30>transmitter freq.: 400.132401 MHztime domain size: 20378 pointswidth: 5597.01 Hz = 13.9879 ppm = 0.274660 Hz/ptnumber of scans: 4
freq. of 0 ppm: 400.130001 MHzprocessed size: 65536 complex pointsLB: 0.100 GF: 0.0000
Fig. S7. 1H NMR (5.5-9.0 ppm, 400MHz, (CD3)2SO) of (MPI-3)-V-TCF
PPM 10 8 6 4 2 0
SpinWorks 4: no title
file: ...оды исследования\ЯМР\ЯМР_ДП\48\fid expt: <zg30>transmitter freq.: 600.133601 MHztime domain size: 33554 pointswidth: 7788.16 Hz = 12.9774 ppm = 0.232108 Hz/ptnumber of scans: 6
freq. of 0 ppm: 600.129999 MHzprocessed size: 8192 complex pointsLB: 0.000 GF: 0.0000
Fig. S8. 1H NMR (600MHz, CDCl3) of (MPI-3)-V-TCF
PPM 8.4 8.0 7.6 7.2 6.8 6.4 6.0 5.6
SpinWorks 4: no title
file: ...оды исследования\ЯМР\ЯМР_ДП\48\fid expt: <zg30>transmitter freq.: 600.133601 MHztime domain size: 33554 pointswidth: 7788.16 Hz = 12.9774 ppm = 0.232108 Hz/ptnumber of scans: 6
freq. of 0 ppm: 600.130010 MHzprocessed size: 8192 complex pointsLB: 0.000 GF: 0.0000
Fig. S9. 1H NMR (5.5-9.0 ppm, 600MHz, CDCl3) of (MPI-3)-V-TCF
PPM 160 120 80 40
SpinWorks 4: no title
file: ...оды исследования\ЯМР\ЯМР_ДП\49\fid expt: <zgdc30>transmitter freq.: 150.918309 MHztime domain size: 50720 pointswidth: 36231.88 Hz = 240.0761 ppm = 0.714351 Hz/ptnumber of scans: 512
freq. of 0 ppm: 150.902810 MHzprocessed size: 131072 complex pointsLB: 3.000 GF: 0.0000
Fig. S10. 13C NMR (150MHz, CDCl3) of (MPI-3)-V-TCF
Table S1. The electric characteristics for the chromophores (MPI-1)-V-TCF and (MPI-3)-V-TCF, calculated in gas phase in aug-cc-pVDZ basis set.
MPI1-V-TCF MPI3-V-TCF
DMA-V-TCF
B3LYP/M06-2X
B3LYP/B3LYP
B3LYP/M06-2X
B3LYP/M06-2X
B3LYP/M06-2X
B3LYP/wB97x
B3LYP/M06-2X
B3LYP/B3LYP
B3LYP/wB97x
α хх 73.2 75.5 47.0 47.0 47.0 72.9 47.0 48.4 46.9α yy 90.9 96.7 99.1 99.1 99.1 93.5 99.1 107.8 93.6α zz 31.8 32.3 23.1 23.1 23.1 32.1 23.1 23.5 23.4α av 65.3 68.2 56.4 56.4 56.4 66.2 56.4 59.9 54.7βxxx -6.67 -9.81 -1.38 -1.38 -1.38 -5.14 -1.38 -2.57 -1.35βxxy 4.64 -1.07 0.43 0.43 0.43 5.09 0.43 -3.24 0.41βxyy 28.81 17.32 28.82 28.82 28.82 33.13 28.82 19.18 27.54βyyy 90.23 68.35 168.65 168.65 168.65 107.63 168.65 147.87 155.49β xxz 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0β xyz 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0β yyz 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0β xzz -0.49 -0.57 -0.36 -0.36 -0.36 -0.47 -0.36 -0.48 0.29β yzz -0.68 -0.86 -1.10 -1.10 -1.10 -0.77 -1.10 -1.57 -1.07β zzz 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0β x 21.65 6.94 27.07 27.07 27.07 27.52 27.07 16.14 25.89β y 94.19 66.42 167.98 167.98 167.98 111.95 167.98 143.07 154.83β z 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0μ x 10.4 10.53 9.9 9.9 9.9 10.74 9.9 10.15 10.14μ y 14.9 15.28 15.8 15.8 15.8 13.23 15.8 16.55 15.61μ z 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
μ tot 18.2 18.56 18.7 18.7 18.7 17.04 18.7 19.42 18.61β ║ 53.74 35.18 94.01 94.01 94.01 62.56 94.01 78.23 86.36
μyβy 1343.40 1044.69 2672.56 2672.56 2672.56 1424.08 2672.56 2447.29 2426.81β total 96.64 66.79 170.14 170.14 170.14 115.29 170.14 143.98 156.98β(0) HRS
37.36 28.30 69.83 69.83 69.83 44.56 69.83 61.22 64.38
Table S2. The electric dynamic (1064 nm) characteristics for the chromophores (MPI-3)-V-TCF and DMA-V-TCF, calculated in aug-cc-pVDZ basis set.
MPI3-V-TCF
DMA-V-TCF
B3LYP/M06-2X
B3LYP/B3LYP
B3LYP/M06-2X
B3LYP/B3LYP
µtot (D) 16.80 17.28 18.58 19.33ω
α(av) 72.27 76.08 60.67 65.72βxxx -6.97 -13.58 -1.70 -3.71βxxy 5.23 4.01 1.88 2.33βxyy 37.86 18.17 39.40 30.64βxzz -0.61 -0.84 -0.44 -0.64βyxx 8.40 7.21 3.09 3.58βyxy 43.17 13.18 42.89 26.96βyyy 132.94 82.37 229.19 210.38βyzz -0.83 -1.21 -1.50 -2.46βzxz -0.70 -0.71 -0.47 -0.58βzyz -0.98 -1.01 -1.58 -2.28βx 33.76 0.50 39.57 23.88βy 137.50 86.37 229.92 210.78βtot 141.58 83.38 233.30 212.13
2ωα(av) 137.03 210.18 95.89 136.47βxxx -3.41 -38.52 -1.03 -8.75βxxy 78.53 39.43 21.86 13.32βxyy 258.37 231.60 153.01 180.29βxzz -2.23 -4.15 -0.93 -1.87βyxx 30.77 45.59 8.68 10.82βyxy 181.56 108.17 114.66 107.39βyyy 546.33 492.68 605.30 764.80βyzz -3.63 -7.14 -2.98 -6.36βzxz -0.82 -0.99 -0.57 -0.81βzyz -1.11 -1.38 -2.01 -3.21βx 209.28 180.75 125.73 121.77βy 606.99 530.86 620.44 773.03βtot 642.06 541.89 633.05 782.56βHRS 226.2 204.0 250.6 316.7DR 5.49 5.13
Estimation of the depolarization ratio (DR).
Laboratory axes: X. Y. Z.
Molecular axes: x. y. z. Molecules lie in the (xy) plane.
Depolarization ratios (DR) is calculated according to
DR=⟨βYYY
2 ⟩
⟨β XYY2 ⟩
,
where ⟨ βYYY2 ⟩ and ⟨ βXYY
2 ⟩ are orientational averages of hyperpolarizability tensor components.
which are proportional to the scattered signal intensities for vertically and horizontally polarized
incident signals. respectively. and are calculated as
⟨ βYYY2 ⟩=1
7β yyy
2 + 935β yxx
2 + 635β yyy β yxx ;
⟨ βXYY2 ⟩= 1
35β yyy
2 +11105
β yxx2 − 2
105β yyy β yxx
.
Table S3. The ratio (R) of intensities of absorption maxima for two bands for the chromophore solutions and chromophore-containing polymers.
Sample R,
before polingR
after poling(MPI-1)-V-TCF, CHCl3 solution (1x10-5 mol/L) 2.18 -
(MPI-1)-V-TCF, dioxane solution (1x10-5 mol/L) 1.37 -
(MPI-1)-V-TCF/PMMA, 20wt% 1.32 1.43
(MPI-1)-V-TCF/PMMA, 30wt% 1.33 1.44
(MPI-3)-V-TCF, CHCl3 solution (2.4x10-5 mol/L) 1.95 -
(MPI-3)-V-TCF, CHCl3 solution (1.9x10-5 mol/L) 1.99 -
(MPI-3)-V-TCF, CHCl3 solution (1x10-5 mol/L) 2.03 -
(MPI-3)-V-TCF, CHCl3 solution (3.9x10-6 mol/L) 2.03 -
(MPI-3)-V-TCF, CHCl3 solution (~7.7x10-6 mol/L) 2.03 -
(MPI-3)-V-TCF, CHCl3 solution (~1.5x10-7 mol/L) 2.26 -
(MPI-3)-V-TCF, dioxane solution (1x10-5 mol/L) 1.25 -
(MPI-3)-V-TCF/PMMA, 20wt% 1.22 1.23
(MPI-3)-V-TCF/PMMA, 25wt% 1.12 1.16
(MPI-3)-V-TCF/PMMA, 30wt% 1.11 1.14
DMA-V-TCF (MPI-3)-V-TCF
DMA-V2-TCF(MPI-3)-V2-TCF
DMA-V3-TCF (MPI-3)-V3-TCF
DMA-V4-TCF (MPI-3)-V4-TCF
DMA-V5-TCF DMA-V5-TCFFig. S11. The Structures of chromophores DMA-Vn-TCF and (MPI-3)-Vn-TCF calculated at the M06-2X/aug-cc-pVDZ level, the values of β for these chromophores are presented in Fig. 4 of the main text.
