Figure S1. 1H NMR spectrum of 2.
Figure S2. 13C (down) and DEPT (up) NMR spectra of 2.
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 ppm 1.703 2.164 3.073 3.904 3.910 7.033 7.039 7.042 7.050 7.053 7.059 7.540 7.542 7.551 7.554 7.556 7.565 7.567 7.614 7.616 7.625 7.628 7.630 7.639 7.641 7.667 7.987 7.992 7.995 8.003 8.007 8.012 8.304 8.305 8.318 8.931 8.945 10.055 5.64 1.99 2.02 3.03 1.96 2.09 1.07 1.10 0.95 2.04 1.01 1.00 0.95 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 ppm 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 ppm 14.18 22.70 23.91 25.81 31.63 53.95 55.60 62.18 112.95 114.07 114.23 122.21 123.01 124.41 125.04 125.32 126.99 132.33 140.01 147.88 158.02 161.29 Published in &KHP3K\V&KHP ± which should be cited to refer to this work.
Figure S3.1H-1H COSY NMR experiment of 2.
Figure S4.1H-1H NOESY NMR experiment of 2.
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 1 2 3 4 5 6 7 8 9 ppm 7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6 8.8 9.0 9.2 ppm 1 2 3 4 5 6 7 8 9
a)
b)
Figure S5.1H-13C HSQC NMR experiment of 2: a) full spectrum; b) aliphatic part.
ppm 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 20 30 40 50 60 70 80 90 100 110 120 130 ppm 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 ppm 15 20 25 30 35 40
a)
b)
Figure S6.1H-13C HMBC NMR experiment of 2: a) full spectrum; b) aromatic part.
1 2 3 4 5 6 7 8 9 ppm 20 40 60 80 100 120 140 160 ppm 6.8 7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6 8.8 9.0 9.2 ppm 60 70 80 90 100 110 120 130 140 150 160
Figure S7.1H NMR spectrum of 3.
Figure S8.13C (down) and DEPT (up) NMR spectra of 3.
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 ppm 1.716 2.242 3.088 3.924 7.545 7.547 7.556 7.558 7.561 7.570 7.572 7.638 7.640 7.649 7.652 7.654 7.664 7.666 7.784 7.787 7.795 7.798 7.997 8.011 8.303 8.304 8.317 8.890 8.904 10.049 5.76 2.36 1.84 2.18 1.12 1.13 3.07 2.05 1.02 1.00 1.04 7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 ppm 30 40 50 60 70 80 90 100 110 120 130 140 150 160 ppm 23.74 25.65 53.85 61.91 112.30 114.43 118.94 122.61 122.67 122.98 125.19 125.66 127.99 133.13 133.22 139.55 155.34 161.50
Figure S9.1H-1H COSY NMR experiment of 3.
Figure S10.1H-1H NOESY NMR experiment of 3.
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 2 3 4 5 6 7 8 9 ppm 7.5 7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 9.0 9.1 ppm 1 2 3 4 5 6 7 8 9
Figure S11.1H-13C HSQC NMR experiment of 3. Figure S12.1H-13C HMBC NMR experiment of 3. ppm 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 30 40 50 60 70 80 90 100 110 120 130 ppm 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 20 40 60 80 100 120 140 160
Figure S13.1H NMR spectrum of 4.
Figure S14.13C (down) and DEPT (up) NMR spectra of 4.
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 ppm 1.385 1.740 2.175 2.242 3.118 3.956 7.558 7.560 7.569 7.572 7.574 7.583 7.585 7.663 7.665 7.674 7.676 7.679 7.688 7.690 7.849 8.038 8.052 8.310 8.324 8.367 8.371 8.374 8.383 8.386 8.390 8.909 8.923 1.22 1.19 0.95 2.06 1.02 2.10 1.00 30 40 50 60 70 80 90 100 110 120 130 140 150 160 ppm 23.73 25.65 53.83 61.94 114.64 122.67 122.92 124.83 125.23 125.69 128.12 133.26 139.67 147.61 156.72 161.98 162.24
Figure S15.1H-1H COSY NMR experiment of 4.
Figure S16.1H-1H NOESY NMR experiment of 4.
ppm 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 2 3 4 5 6 7 8 9 ppm 7.5 7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 9.0 9.1 ppm 2 3 4 5 6 7 8 9
Figure S17.1H-13C HSQC NMR experiment of 4. Figure S18.1H-13C HMBC NMR experiment of 4. 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 30 40 50 60 70 80 90 100 110 120 130 ppm 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 20 40 60 80 100 120 140 160
Figure S19.1H NMR spectrum of 7-NMe (contains i-PrOH).
Figure S20.13C (down) and DEPT (up) NMR spectra of 7-NMe (contains i-PrOH). 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 ppm 3.794 6.684 6.725 7.402 7.412 7.420 7.440 7.448 7.458 7.511 7.553 7.558 7.563 7.587 7.592 7.594 7.618 7.623 7.643 7.653 7.658 7.662 7.665 7.681 7.689 7.696 7.719 7.725 8.188 8.190 3.09 0.98 2.04 1.21 0.89 3.03 0.98 1.00 6.8 6.9 7.0 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.3 8.4 ppm 50 60 70 80 90 100 110 120 130 140 150 160 170 180 ppm 45.47 104.90 115.75 119.33 124.13 126.25 128.98 129.51 129.98 130.86 132.60 133.35 135.23 142.03 151.70 184.70
Figure S21.1H-1H COSY NMR experiment of 7-NMe (contains i-PrOH).
Figure S22.1H-1H NOESY NMR experiment of 7-NMe (contains i-PrOH).
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 ppm 6.6 6.8 7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6 ppm 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0
Figure S23.1H-13C HSQC NMR experiment of 7-NMe (contains i-PrOH).
Figure S24.1H-13C HMBC NMR experiment of 7-NMe (contains i-PrOH).
ppm 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 ppm 40 50 60 70 80 90 100 110 120 130 ppm 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 ppm 60 80 100 120 140 160 180
Figure S26: Change of the relative energy (M06-2X/def2-TZVP) of the tautomers in gas phase of the parent compound 8 (left), 4 (center) and 4H+ ULJKW 7KHYDOXHVRI¨(¨(=3(DQG ¨¨*DUHJLYHQLQNFDOPROXQLWV
Figure S27: Change of the relative energy (M06-2X/def2-TZVP) of the tautomers in acetonitrile (PCM field) of the parent compound 8 (left), 4 (center) and 4H+(right). The values RI¨(¨(=3(DQG¨¨*DUHJLYHQLQNFDOPROXQLWV
Compound reference 2 3 4
Chemical formula C23H25N3O2 C23H22N4O C22H22N4O3
Formula Mass 375.46 370.45 390.44
Crystal system Monoclinic Triclinic Triclinic
a/Å 34.716(8) 5.1014(8) 5.2175(7) b/Å 5.994(4) 11.5731(17) 10.7215(16) c/Å 20.442(6) 16.653(3) 17.295(3) Į/° 90 92.321(12) 82.197(12) ȕ/° 105.63(2) 93.662(13) 81.572(12) Ȗ/° 90 101.162(12) 89.056(12)
Unit cell volume/Å3 4096(3) 961.2(3) 948.1(2)
Temperature/K 290(2) 200(2) 200(2)
Space group C2/c P1¯ P1¯
No. of formula units per unit cell, Z 8 2 2
Radiation type 0R.Į &X.Į 0R.Į
Absorption coefficient, ȝ/mm-1 0.079 0.640 0.093
No. of reflections measured 7696 11643 12143
No. of independent reflections 4030 3169 3343
Rint 0.0833 0.0763 0.1473
Final R1values (I > 2ı(I)) 0.0564 0.0439 0.0605
Final wR(F2) values (I > 2ı(I)) 0.1167 0.1134 0.1530
Final R1values (all data) 0.181 0.0936 0.1476
Final wR(F2) values (all data) 0.1614 0.1360 0.1832
Table S2. Observed and calculated (PBE0/6-31G**) absorption maxima of compounds 1-8 in acetonitrile.
Structure Omax[nm]
observed calculated predicted*
1E 417 428 419 1K 452 1EH+ 403 1KH+ 495 475 477 1ZW 462 5E 408 414 401 5K 468 450 446 2E 419 434 426 2K 484 2EH+ 417 2KH+ 517 516 528 2ZW 464 6E 412 422 411 6K 495 484 488 3E 444 462 561 3K 449 3EH+ 430 3KH+ 472 472 473 3ZW 555 505 514 7E 429 446 441 7K 459 446 441 4E 466 496 503 4K 460 4EH+ 450 4KH+ 472 476 478 4ZW 593 561 584 8E 435 475 477 8K 468 456 453
* Predicted using the linear regression between observed and calculated values given in Figure S25.
