Supporting Information for Functional Group Transformations in Derivatives of 1,4-Dihydrobenzo[1,2,4]triazinyl Radical Agnieszka Bodzioch, a, Minyan Zheng, a Piotr Kaszyński, a,b * Greta Utecht a a Organic Materials Research Group Department of Chemistry, Vanderbilt University, ashville, T 37235 b Faculty of Chemistry, University of Łódź, Tamka 12, 91403 Łódź, Poland Table of Content: 1. 1 H MR and 13 C MR spectra for selected compounds.s2 2. Thermodynamic data for formation of 32.S66 3. Partial data for TD-DFT calculation (B3LYP/6-31G(d,p)) for 1 S67 4. Theoretical hfcc values for model radicals S75 5. Simulation of EPR spectra S75 6. Archive data for DFT calculations S76 S 1
1. 1 H MR and 13 C MR spectra for selected compounds 6a Ph(O)CO CF 3 H H OC(O)Ph S 2
6b S 3
Ph(O)CO CF 3 H H OCH 2Ph S 4
6c S 5
I CF 3 H H OCH 2 Ph S 6
6d S 7
I CF 3 H H I S 8
6e S 9
CF 3 H H O 2 S 10
7a S 11
Ph(O)CO I H H OC(O)Ph S 12
7d S 13
I I H H I S 14
8d S 15
I F H H I S 16
9a S 17
Ph(O)CO H H OC(O)Ph S 18
9b S 19
Ph(O)CO H H OCH 2 Ph S 20
11a S 21
O H CF 3 OC(O)Ph S 22
11b S 23
O H CF 3 OCH 2 Ph S 24
11d S 25
O H CF 3 I S 26
11e S 27
S 28
12a S 29
O H I OC(O)Ph S 30
12d S 31
O H I I S 32
13d S 33
O H F I S 34
14a S 35
O H OC(O)Ph S 36
14b S 37
O H OCH 2 Ph S 38
15a S 39
Cl CF 3 OC(O)Ph S 40
15b S 41
Cl CF 3 OCH 2 Ph S 42
S 43
15d Cl CF 3 I S 44
15e S 45
Cl CF 3 O 2 S 46
16d S 47
Cl I I S 48
17d S 49
Cl F I S 50
18a S 51
Cl OC(O)Ph S 52
18b S 53
Cl OCH 2 Ph S 54
22a S 55
F 3 C O 2 I S 56
22b S 57
F 3 C O 2 OCH 2 Ph S 58
23a S 59
F 3 C O 2 H 2 I S 60
23b S 61
F 3 C O 2 H 2 OCH 2 Ph S 62
26 S 63
O H H OCH 2 Ph OCH 2 Ph S 64
S 65
2. Thermodynamic data for formation of 1,3-diphenyl-1,4-dihydrobenzo[1,2,4]triazine 32 Z 6 7 8 8a 5 Ph 1 4 3 2 Ph Z H Ph Ph 29 Me 3 H 31 Me 3 H Z Ph Z H Ph 29[H + ] H Ph 31[H + ] Ph H Me 3 a, Z = H b, Z = OH c, Z = C Figure S1. Proposed mechanism for the formation of 1,3-diphenyl-1,4- dihydrobenzo[1,2,4]triazine 32. Z Ph 32 H Ph Table S1. Thermodynamic data for formation of 1,4-dihydrobenzo[1,2,4]triazine 32 from 29. Z ΔH (upper) and ΔG 298 (lower) in CH 2 Cl 2 /kcal mol -1 a,h 36.0 38.6 b,oh 33.9 36.6 c,c 37.4 40.0 29 30 29 31 31 31[H + ] 31[H + ] 32 29 29[H + ] 29[H + ] 30[H + ] 29[H + ] 31[H + ] 29 32 9.0 11.7 7.7 10.7 13.1 15.9 7.1 7.5 7.7 7.8 11.9 12.0-35.3-35.2-34.0-34.0-43.8-43.7 5.7 6.5 1.4 2.6 10.6 11.2 14.0 16.7 16.8 20.5 17.4 21.5 10.3 12.7 14.0 15.9 14.4 16.7-19.2-16.0-18.6-15.6-18.8-15.8 S 66
3. Partial data for TD-DFT calculation (B3LYP/6-31G(d,p)) for 1r and 4x. α-homo-1, E = -5.71 ev α -HOMO, E = -4.78 ev α -LUMO, E = -1.84 ev α -LUMO+1, E = -1.60 ev β -HOMO-1, E = -5.96 ev β-homo, E = -5.63 ev β-lumo, E = -2.85 ev β-lumo+1; E = -1.72 ev Figure S2. B3LYP/6-31G(2d,p) derived contours and energies of frontier molecular orbitals for 1r. S 67
β-homo-1; E = -6.14 ev Figure S3. B3LYP/6-31G(2d,p) derived contour and energies of frontier molecular orbitals for 4x. 20 10 3 15 10 3! /L mol -1 cm -1 10 10 3 5 10 3 4n 1r 0 300 400 500 600 wavelength /nm Figure S4. Magnified absorption spectra for 1r and 4n. Excitation energies and oscillator strength 1r Excited State 1: 2.040-A 1.9849 ev 624.63 nm f=0.0106 <S**2>=0.790 143A ->144A 0.87819 143A ->146A -0.23075 140B ->143B -0.11657 142B ->143B -0.33200 This state for optimization and/or second-order correction. Total Energy, E(TD-HF/TD-KS) = -1848.13153993 Copying the excited state density for this state as the 1-particle RhoCI density. Excited State 2: 2.354-A 142A ->144A 0.20229 2.2127 ev 560.34 nm f=0.0218 <S**2>=1.135 S 68
143A ->144A 0.26523 143A ->145A -0.27696 140B ->143B 0.17577 141B ->143B -0.27170 142B ->143B 0.78147 142B ->144B 0.16089 Excited State 3: 2.614-A 141A ->145A -0.26513 142A ->144A 0.17077 143A ->144A 0.17807 143A ->145A 0.56911 141B ->143B 0.53109 141B ->145B 0.25879 142B ->143B 0.31906 142B ->144B 0.15769 2.3539 ev 526.72 nm f=0.0115 <S**2>=1.458 Excited State 4: 3.208-A 2.5519 ev 485.84 nm f=0.0148 <S**2>=2.322 142A ->144A 0.58297 142A ->146A 0.20242 143A ->144A -0.11680 143A ->146A 0.12459 141B ->143B -0.10938 142B ->143B -0.33173 142B ->144B 0.56608 142B ->145B 0.12219 142B ->146B 0.18415 Excited State 5: 2.080-A 143A ->145A -0.60675 134B ->143B 0.11280 137B ->143B 0.36412 140B ->143B -0.21578 141B ->143B 0.61202 Excited State 6: 2.127-A 141A ->145A 0.13864 143A ->145A 0.29430 133B ->143B -0.13902 134B ->143B 0.20745 135B ->143B 0.15660 137B ->143B 0.79185 140B ->143B -0.15720 141B ->143B -0.27842 141B ->145B -0.12541 2.6278 ev 471.83 nm f=0.3651 <S**2>=0.832 2.7626 ev 448.79 nm f=0.0944 <S**2>=0.881 S 69
Excited State 7: 2.808-A 141A ->145A 0.47002 143A ->145A 0.23876 143A ->147A 0.18140 143A ->148A 0.12735 135B ->143B -0.20872 137B ->143B -0.24204 140B ->143B -0.43408 141B ->143B 0.21039 141B ->144B 0.14853 141B ->145B -0.42208 142B ->143B 0.14618 2.9033 ev 427.04 nm f=0.0066 <S**2>=1.721 Excited State 8: 2.480-A 3.0945 ev 400.66 nm f=0.0020 <S**2>=1.287 141A ->145A 0.28716 143A ->146A -0.11167 131B ->143B 0.14798 135B ->143B 0.22675 140B ->143B 0.68774 141B ->143B 0.33024 141B ->145B -0.31692 142B ->143B -0.14613 Excited State 9: 2.152-A 3.1900 ev 388.66 nm f=0.0505 <S**2>=0.908 143A ->144A 0.22154 143A ->146A 0.79248 143A ->147A -0.39014 143A ->148A -0.11883 143A ->151A -0.10417 143A ->152A -0.16864 130B ->143B -0.13247 Excited State 10: 2.271-A 138A ->144A 0.10066 141A ->145A -0.10747 142A ->146A -0.11970 143A ->144A 0.15459 143A ->145A -0.17572 143A ->146A 0.32543 143A ->147A 0.77253 143A ->148A 0.16222 143A ->153A -0.21047 142B ->146B -0.11258 Excited State 11: 3.002-A 134A ->144A 0.13781 3.3127 ev 374.27 nm f=0.0145 <S**2>=1.039 3.4274 ev 361.74 nm f=0.0256 <S**2>=2.004 S 70
138A ->144A -0.18986 139A ->150A 0.17271 140A ->144A -0.14711 142A ->146A 0.26326 142A ->151A 0.10194 142A ->152A 0.11348 142A ->153A 0.14211 143A ->146A 0.12881 143A ->147A 0.24613 143A ->148A -0.31821 135B ->144B 0.17348 138B ->150B 0.17238 139B ->143B 0.39586 139B ->151B 0.10523 140B ->144B -0.23595 142B ->144B -0.19051 142B ->146B 0.30215 142B ->152B -0.14999 142B ->153B -0.12062 Excited State 12: 2.367-A 142A ->146A 0.12135 143A ->146A 0.11705 143A ->147A -0.21236 143A ->148A 0.80344 143A ->152A 0.11135 133B ->143B 0.13565 135B ->143B 0.24109 140B ->144B -0.13101 142B ->146B 0.14126 Excited State 13: 2.423-A 138A ->144A 0.18692 142A ->144A 0.20869 142A ->146A -0.17528 143A ->146A -0.12495 139B ->143B 0.85391 139B ->144B 0.10412 140B ->143B -0.10007 142B ->146B -0.14485 Excited State 14: 2.106-A 142A ->144A -0.62510 131B ->143B 0.10023 135B ->143B 0.15717 139B ->143B 0.18866 3.4445 ev 359.94 nm f=0.0021 <S**2>=1.150 3.4735 ev 356.95 nm f=0.0077 <S**2>=1.218 3.5515 ev 349.10 nm f=1.2240 <S**2>=0.859 S 71
4x 140B ->143B -0.11171 141B ->144B -0.10400 142B ->144B 0.64872 Excited State 1: 2.052-A 2.1358 ev 580.51 nm f=0.0046 <S**2>=0.803 91A -> 92A 0.92014 90B -> 91B -0.32776 This state for optimization and/or second-order correction. Total Energy, E(TD-HF/TD-KS) = -1125.70005208 Copying the excited state density for this state as the 1-particle RhoCI density. Excited State 2: 2.107-A 91A -> 92A 0.31222 91A -> 94A -0.11085 88B -> 91B -0.16389 89B -> 91B -0.20450 90B -> 91B 0.87642 Excited State 3: 2.060-A 87B -> 91B 0.71035 89B -> 91B 0.63963 90B -> 91B 0.18268 Excited State 4: 2.135-A 91A -> 93A -0.22760 91A -> 94A -0.27289 87B -> 91B 0.61323 88B -> 91B -0.15199 89B -> 91B -0.61286 90B -> 91B -0.15353 Excited State 5: 2.252-A 90A -> 92A 0.16311 91A -> 93A 0.59481 91A -> 94A 0.57542 84B -> 91B 0.13943 87B -> 91B 0.18886 88B -> 91B -0.28254 89B -> 91B -0.22810 90B -> 92B -0.13707 Excited State 6: 2.687-A 90A -> 92A -0.34056 91A -> 93A 0.62463 2.4837 ev 499.19 nm f=0.0374 <S**2>=0.860 2.8692 ev 432.12 nm f=0.0292 <S**2>=0.810 3.0407 ev 407.75 nm f=0.0433 <S**2>=0.890 3.0813 ev 402.38 nm f=0.0836 <S**2>=1.018 3.2154 ev 385.60 nm f=0.0074 <S**2>=1.554 S 72
91A -> 94A -0.29960 91A -> 96A 0.14266 86B -> 95B 0.10383 88B -> 91B 0.26997 90B -> 91B 0.10194 90B -> 92B 0.40552 Excited State 7: 2.928-A 88A -> 95A 0.10174 90A -> 92A -0.44197 90A -> 97A 0.11685 91A -> 93A -0.34143 91A -> 94A 0.47807 91A -> 97A 0.13395 86B -> 95B 0.13130 88B -> 91B -0.24281 90B -> 92B 0.46429 90B -> 97B -0.10031 Excited State 8: 2.223-A 90A -> 92A 0.10515 91A -> 93A -0.17333 91A -> 94A 0.42858 91A -> 96A 0.14984 86B -> 91B -0.12843 87B -> 91B 0.13654 88B -> 91B 0.74430 89B -> 91B -0.19191 90B -> 91B 0.14607 Excited State 9: 2.468-A 85A -> 93A -0.15583 89A -> 94A 0.15742 91A -> 95A 0.41325 91A -> 96A 0.64276 91A -> 97A -0.15106 84B -> 91B 0.22570 85B -> 93B 0.17772 88B -> 91B -0.23000 89B -> 91B 0.20099 89B -> 94B -0.20733 89B -> 97B -0.10009 90B -> 94B 0.10756 Excited State 10: 2.149-A 91A -> 95A 0.86401 3.2588 ev 380.46 nm f=0.0130 <S**2>=1.894 3.3370 ev 371.55 nm f=0.0423 <S**2>=0.985 3.6488 ev 339.79 nm f=0.0622 <S**2>=1.273 3.7847 ev 327.59 nm f=0.0018 <S**2>=0.904 S 73
91A -> 96A -0.31460 84B -> 91B -0.24822 90B -> 92B 0.12299 Excited State 11: 2.510-A 85A -> 93A -0.11430 88A -> 94A 0.10653 89A -> 94A 0.10393 90A -> 96A 0.12271 91A -> 96A -0.23109 91A -> 97A -0.54753 84B -> 92B 0.18191 85B -> 93B 0.11895 86B -> 91B 0.55045 86B -> 95B 0.10728 88B -> 91B 0.12963 88B -> 94B 0.13610 90B -> 96B 0.14722 Excited State 12: 2.316-A 90A -> 92A 0.16214 91A -> 96A 0.22255 91A -> 97A 0.37733 84B -> 92B -0.11382 85B -> 93B -0.10686 86B -> 91B 0.77541 88B -> 91B 0.11242 Excited State 13: 2.088-A 84B -> 91B -0.15308 85B -> 91B 0.94893 87B -> 91B 0.10410 Excited State 14: 2.534-A 85A -> 93A 0.18207 85A -> 94A -0.13973 89A -> 94A -0.21623 89A -> 96A 0.10233 90A -> 92A -0.23415 91A -> 94A -0.15652 91A -> 95A 0.17500 91A -> 97A -0.31931 84B -> 91B 0.62289 85B -> 91B 0.10775 85B -> 93B -0.23866 89B -> 94B 0.21697 3.8155 ev 324.95 nm f=0.0053 <S**2>=1.325 3.8798 ev 319.56 nm f=0.0034 <S**2>=1.091 3.9964 ev 310.24 nm f=0.0027 <S**2>=0.840 4.0092 ev 309.25 nm f=0.0140 <S**2>=1.356 S 74
90B -> 92B -0.13194 4. Theoretical hfcc values for model radicals Table S2. Theoretical hyperfine coupling constants (G) for selected radicals. X F 3 C 6 7 8 5 1 4 3 2 Y Heterocyclic ring CF 3 at (1) at C(3) compound a (1) a (2) a (4) a H(5) a H(6) a H(8) a F a Ho a Hm a Hp a Ho a Hm 1e X=H, Y=O 2 1t X=H, Y=H 2 1y X=H 2, Y=O 2 1 X=H, Y=OMe 1 X=H, Y=O- a 5.54 3.67 4.32-1.88-0.46-1.04 4.05-0.92 0.69-0.86 0.37-0.23 5.34 4.23 4.03-1.82-0.47-1.21 3.98-0.96 0.69-0.91 0.36-0.20 5.75 3.50 4.21-1.89-0.53-1.24 3.62-0.88 0.60 0.34-0.22 5.36 4.18 4.07-1.85-0.47-1.18 3.91-0.95 0.69-0.90 0.37-0.20 3.78 6.07 1.84-0.80-0.62-1.48 1.21-1.05 0.64-1.15 0.67-1.31 B3LYP/EPR-II//B3LYP/6-31G(2d,p). The hfcc calculated by averaging values for equivalent nuclei. 5. Simulation of EPR spectra Simulation of the EPR spectra was done with the PEST program (EPR-WinSim.2002 version 0.98 for Windows; available at: http://www.niehs.nih.gov/research/resources/software/toxpharm/tools/index.cfm) using results of B3LYP/EPR-II//B3LYP/6-31G(2d,p) for initial input. The resulting hfcc values were perturbed until the global minimum for the fit was achieved. Spectra used for simulation were generated by reflection of the left half of each spectrum. S 75
Figure S5. A comparison for experimental, simulate and difference spectra for selected radicals. 6. Archive files for DFT calculations 1e 1\1\GIC-OCTOPUS\FOpt\UB3LYP\6-31G(2d,p)\C20H12F34O2(2)\PIOTR\20-Feb- 2014\0\\#P B3LYP/6-31G(2d,p) FOpt=tight freq(noraman) SCF=Direct #P Ge om=(odistance,oangle) fcheck\\7-cf3-1-ph-3-pho2-benzotrazinyl, C1\\ 0,2\C,-3.0106585959,0.0838939092,-1.5062634798\C,-1.6386736528,0.10314 71952,-1.2863349008\C,-1.1489623006,-0.038815161,0.0157290486\C,-2.046 5003683,-0.144628786,1.1145349986\C,-3.4293990764,-0.1669583838,0.8518 057649\C,-3.9088963214,-0.0591375693,-0.4396519841\H,-0.9640579368,0.2 375909437,-2.1192398916\,0.2090080946,-0.0463686294,0.3329673874\,-1.6018192995,-0.1952831679,2.4039238446\H,-4.0977675231,-0.2534029048,1.7003254195\C,-0.281399169,-0.0825944186,2.5701803933\,0.6467254972,- 0.0047108027,1.6160968437\C,1.2522704671,-0.0313835252,-0.6445572573\C,1.2709375644,-0.9742742059,-1.6743027564\C,2.3093360305,-0.9555565391 S 76
,-2.6017263521\C,3.3290026705,-0.0113290366,-2.4975007341\C,3.31156047 92,0.9157356671,-1.4558708669\C,2.2764517436,0.9096489452,-0.526910679 9\H,0.4923281747,-1.7254528873,-1.7356986463\H,2.3248645045,-1.6910285 091,-3.398792943\H,4.1043659878,1.6507466232,-1.3668784698\H,2.2506463 175,1.6198327919,0.2901934305\C,0.2370741095,-0.0521630444,3.96344661\ C,1.6149516012,-0.0065279654,4.2225397048\C,2.0863556865,0.0243392442, 5.5272278057\C,1.1679727533,0.0083066475,6.5727409991\C,-0.203515819,- 0.0386734899,6.3461821661\C,-0.6642830441,-0.0691099778,5.0368439782\H,2.3086606147,0.0007052974,3.3918641007\H,3.1440750683,0.0584200854,5. 7507616988\H,-0.8807387434,-0.0498040294,7.1895290484\H,-1.7249825282, -0.1065006489,4.8250602549\H,-4.9751245752,-0.0668137697,-0.6327575643 \C,-3.5425889933,0.1789838603,-2.9099683372\F,-4.654209757,0.934743033 6,-2.9668077112\F,-3.8741824079,-1.0344253581,-3.398631967\F,-2.642988 9192,0.7099960562,-3.7570264337\,1.662673165,0.0413813334,7.957144440 9\O,0.8324610799,0.0245283152,8.8583964122\O,2.8758412469,0.0841807631,8.1264884161\H,4.1368461745,-0.0016059015,-3.2211337913\\Version=EM64 L-G09RevC.01\State=2-A\HF=-1438.266652\S2=0.766304\S2-1=0.\S2A=0.75016 7\RMSD=4.844e-09\RMSF=4.692e-07\Dipole=0.2324739,-0.0149055,-2.1947606 \Quadrupole=13.7049193,10.465277,-24.1701963,1.9404708,-21.3860076,1.8 98545\PG=C01 [X(C20H12F34O2)]\\@ 1r 1\1\GIC-OCTOPUS\FOpt\UB3LYP\6-31G(2d,p)\C36H21F33(2)\PIOTR\23-Mar-20 14\0\\#P B3LYP/6-31G(2d,p) FOpt=tight freq(noraman) SCF=Direct #P Geom =(odistance,oangle) fcheck\\7-cf3-1,3-(phccph)-benzotrazinyl, C1\\0, 2\,-0.5431912564,0.1365291697,0.4086900353\,-0.1162443034,0.08217311 62,-0.8794452506\C,-1.0551021565,0.121688635,-1.8291895181\,-2.376298 8935,0.2095694731,-1.6450880667\C,-2.8061291777,0.1509737752,-0.353557 7917\C,-1.8971423815,0.0761335256,0.7392950864\C,-2.3721712868,-0.0932 36381,2.0433627484\C,-3.7428192906,-0.1189803875,2.2752273053\C,-4.653 0576479,0.0029651482,1.2164267592\C,-4.1873528606,0.1297276368,-0.0781 022065\C,-0.553391552,0.0815456123,-3.2235152587\C,0.8205424962,0.0517 849788,-3.5050295683\C,1.27299456,0.0117493058,-4.8139849225\C,0.36346 0977,0.0019392213,-5.8885187166\C,-1.0137627545,0.0339310556,-5.601899 9868\C,-1.4621067807,0.0727114716,-4.2909588607\C,0.5065654174,0.20814 60117,1.368713814\C,1.6283882833,-0.6122743989,1.2155642242\C,2.674078 6675,-0.5314215227,2.1208842049\C,2.6297219624,0.3744615479,3.19775832 24\C,1.5005345948,1.2035660853,3.3278453506\C,0.4524077621,1.125871103,2.4228453597\H,-4.864539432,0.1953544439,-0.9215195618\H,-5.717010803 7,-0.0237764954,1.418646618\H,-1.6871170562,-0.2162915523,2.8699686973 \H,-2.5218771054,0.0969382493,-4.0706405464\H,-1.7235501247,0.02696872 45,-6.4214304824\H,2.3366134679,-0.009313836,-5.0231492445\H,1.5274714 975,0.065621868,-2.6850095291\H,-0.3955717859,1.7932006638,2.518957643 6\H,1.4611310647,1.9211167157,4.1390563469\H,3.5393031338,-1.174105547 3,2.0064777799\H,1.6657914235,-1.3032355257,0.3830758578\C,-4.25150964 73,-0.2334719588,3.6851490452\F,-3.3839338628,-0.8828678931,4.48302630 23\F,-5.4253911581,-0.88811639,3.7396735464\F,-4.4583061458,0.97941933 27,4.2422291578\C,3.7023289988,0.4566304862,4.1263450837\C,4.617610825,0.5297723923,4.9200246007\C,0.8260753262,-0.0375677045,-7.2322663316\ C,1.2205736277,-0.0707973886,-8.3797556643\C,5.6891975403,0.6209047204,5.8524629764\C,5.6488817869,1.5643391393,6.8951422855\C,6.696912173,1.6525304824,7.8033042574\C,7.7993043077,0.8053726605,7.6896736145\C,7. 8487318807,-0.1339036906,6.6595626028\C,6.8052291295,-0.228796112,5.74 66697098\H,4.7901919904,2.2208308514,6.9796018622\H,6.6536254162,2.384 853291,8.6028611094\H,8.6159230645,0.8767023465,8.4004317717\H,8.70396 95739,-0.7953185676,6.566954275\H,6.8394517723,-0.9572732191,4.9443928 461\C,1.6827117965,-0.1103020708,-9.7254279358\C,3.0590596694,-0.18174 77325,-10.0074946226\C,3.5059683642,-0.2211594119,-11.3227982338\C,2.5 S 77
934415794,-0.189883913,-12.3774077274\C,1.2264929653,-0.1186122102,-12.1087733895\C,0.771021789,-0.0791732363,-10.7964070393\H,3.7648418858, -0.2058111798,-9.1848019305\H,4.5705305527,-0.2763362975,-11.526082165 \H,2.9457383294,-0.2207045394,-13.4031613963\H,0.5121427308,-0.0938030 294,-12.9253088977\H,-0.2905719197,-0.0240100496,-10.583081356\\Versio n=em64l-g09revc.01\state=2-a\hf=-1848.2044839\s2=0.766994\s2-1=0.\s2a= 0.750196\RMSD=1.703e-09\RMSF=8.807e-07\Dipole=1.1046142,0.0473105,0.07 68411\Quadrupole=3.0697183,-13.274567,10.2048487,-3.4317666,13.6638551,6.0239954\PG=C01 [X(C36H21F33)]\\ 1t 1\1\GIC-OCTOPUS\FOpt\UB3LYP\6-31G(2d,p)\C20H14F34(2)\PIOTR\21-Feb-20 14\0\\#P B3LYP/6-31G(2d,p) FOpt=tight freq(noraman) SCF=Direct #P Geom =(odistance,oangle) fcheck\\7-cf3-1-ph-3-phh2-benzotrazinyl, C1\\0, 2\C,-1.9157441315,0.0819787682,-2.5772975533\C,-0.6954416914,0.0958837 328,-1.9124492012\C,-0.6665681544,-0.0375660779,-0.5201374533\C,-1.878 8606404,-0.1257125749,0.2206041258\C,-3.0957492178,-0.1441352865,-0.49 03539692\C,-3.1185050672,-0.0469018321,-1.8680194707\H,0.2184252045,0. 2210981933,-2.4748316769\,0.5053145887,-0.0509143662,0.2326825668\,- 1.8908457527,-0.1645855098,1.5816682629\H,-4.0088605637,-0.2181744998, 0.0885866209\C,-0.7033008189,-0.0490480352,2.1876410607\,0.4935028687,0.0132214474,1.5898119799\C,1.8139757837,-0.0624866726,-0.3380594278\ C,2.1574678835,-1.0035915928,-1.3114761014\C,3.4472968677,-1.010928147 2,-1.835882188\C,4.3958608006,-0.0944239511,-1.3862197675\C,4.05068110 84,0.8303204444,-0.4009846534\C,2.7639294083,0.8497606196,0.1261988336 \H,1.4276978716,-1.7345153049,-1.6389418335\H,3.7114413221,-1.74582105 02,-2.588867021\H,4.7847803834,1.5442510907,-0.0424975825\H,2.48197571 92,1.5567972541,0.8961941277\C,-0.6815411759,0.0034069512,3.6628530158 \C,0.522833869,0.0476252412,4.3811925095\C,0.5278831586,0.0966741909,5.7654396583\C,-0.6775472762,0.1037897969,6.486778259\C,-1.8844516738,0.0578431556,5.7704106598\C,-1.8830722942,0.0086037322,4.3858356825\H,1.4597639871,0.0353196813,3.8379226884\H,1.4713962357,0.1302546871,6.30 30819686\H,-2.8264778452,0.0645308805,6.3117031267\H,-2.8168644421,-0. 0296468207,3.8384474577\H,-4.0602231629,-0.0513866335,-2.4042547316\C, -1.9481137445,0.164259939,-4.0767323056\F,-0.8213083993,0.7007001247,- 4.5808588011\F,-2.0864107277,-1.0544706003,-4.6435421529\F,-2.98309564 02,0.9075500032,-4.512347321\,-0.6762179116,0.2137462022,7.8741639342 \H,-1.504892578,-0.1421317362,8.3297453602\H,0.1656019211,-0.114397434 4,8.3264335657\H,5.3999289277,-0.1046300104,-1.7964682531\\Version=EM6 4L-G09RevC.01\State=2-A\HF=-1289.1179061\S2=0.765879\S2-1=0.\S2A=0.750 161\RMSD=7.030e-09\RMSF=3.690e-07\Dipole=0.9108547,-0.3415122,1.276565 3\Quadrupole=3.8934775,-9.8572128,5.9637353,1.2483947,-5.7202342,-2.60 20576\PG=C01 [X(C20H14F34)]\\@ 1y 1\1\GIC-OCTOPUS\FOpt\UB3LYP\6-31G(2d,p)\C20H13F35O2(2)\PIOTR\18-Apr- 2014\0\\#P B3LYP/6-31G(2d,p) FOpt=tight SCF=Direct #P Geom=(oDistance,oAngle) fcheck\\7-cf3-1-h2ph-3-pho2-benzotrazinyl, C1\\0,2\C,-3.02 29967549,0.0963763989,-1.4988421507\C,-1.6494516982,0.1199597669,-1.28 05263155\C,-1.1570683729,-0.0285717593,0.0193286704\C,-2.0529206918,-0.1434098271,1.1195490897\C,-3.4354565151,-0.1691339312,0.8587702081\C, -3.9179062839,-0.0562180952,-0.4320308857\H,-0.9746346366,0.2628943546,-2.1123984565\,0.2018693341,-0.0385450488,0.3310381133\,-1.60518487 67,-0.1977650581,2.4076843474\H,-4.102473322,-0.261606107,1.7077669352 \C,-0.2842319383,-0.0834510877,2.5692599862\,0.64212361,-0.0053113477,1.6140553411\C,1.2375915328,-0.0197604266,-0.6518689412\C,1.266620966 9,-0.9618360366,-1.6824743727\C,2.2973563749,-0.9494167343,-2.61134370 74\C,3.331317622,-0.0031589517,-2.525427332\C,3.2998601972,0.926227484 S 78
,-1.4719971626\C,2.2671005282,0.9177970985,-0.5478607184\H,0.493124515,-1.7184553651,-1.746740279\H,2.3103990606,-1.6873884212,-3.407507034\ H,4.091012554,1.664979093,-1.3869526041\H,2.2516318526,1.6314426362,0. 2668703911\C,0.2369482363,-0.0538718828,3.9618965951\C,1.6146720785,0. 0063126058,4.2192219673\C,2.0877692271,0.0374997683,5.5232398022\C,1.1 715246631,0.006999779,6.570555651\C,-0.199799211,-0.0548971238,6.34570 24264\C,-0.6620083594,-0.0852849015,5.0369853561\H,2.306208304,0.02516 79873,3.3868686931\H,3.1453448707,0.0831275765,5.7454630844\H,-0.87578 3622,-0.0772359752,7.189809862\H,-1.7223781623,-0.1335247371,4.8259184 494\H,-4.9840651943,-0.0665342616,-0.6238058731\C,-3.5509503801,0.1896 835414,-2.9035467693\F,-4.7416095951,0.8142694882,-2.9466838234\F,-3.7 337094912,-1.031536194,-3.4501816491\F,-2.7098437153,0.8557881838,-3.7 154314942\,1.6678764422,0.0407620192,7.9537497488\O,0.839627694,0.011 7732707,8.8567671849\O,2.8809609989,0.0963256103,8.121954286\,4.33004 37745,0.0492636289,-3.4902356321\H,5.1939294322,0.4799588768,-3.192685 6501\H,4.4947909513,-0.8146408947,-3.9871773381\\Version=EM64L-G09RevC.01\State=2-A\HF=-1493.628482\S2=0.765523\S2-1=0.\S2A=0.750153\RMSD=1. 642e-09\RMSF=3.235e-07\Dipole=1.0710629,-0.2398012,-2.5768699\Quadrupo le=20.3142386,7.5448894,-27.8591281,0.1089997,-27.879788,4.6413351\pg= C01 [X(C20H13F35O2)]\\@ 1 X = OAc, Y = OMe 1\1\GIC-OCTOPUS\FOpt\UB3LYP\6-31G(2d,p)\C22H183O3(2)\PIOTR\23-Feb-20 14\0\\#P B3LYP/6-31G(2d,p) FOpt=tight freq(noraman) SCF=Direct #P Geom =(odistance,oangle) fcheck\\7-cf3-1-phoac-3-phome-benzotrazinyl, C1\ \0,2\C,-1.8497409591,0.1478571578,-2.4838426682\C,-0.6306190285,0.1901 106879,-1.8191807786\C,-0.5911242249,0.0134835561,-0.4296164662\C,-1.7 972644507,-0.1508893681,0.3069742116\C,-3.0128061781,-0.2023519456,-0. 4006169678\C,-3.0408543013,-0.0618615719,-1.7774839378\H,0.2816790374, 0.3705226989,-2.3718722553\,0.5821666259,0.0213632571,0.3237012978\, -1.8043712675,-0.2321346517,1.6707769003\H,-3.9184127727,-0.3394490171,0.1792752349\C,-0.623605821,-0.0840885686,2.2761918096\,0.569454234, 0.0452747877,1.6841546087\C,1.8879247791,0.0721051288,-0.2442352104\C, 2.2652630881,-0.8178017333,-1.2526414309\C,3.5526552462,-0.7654483494, -1.7744165981\C,4.4647403364,0.1610211413,-1.2795530281\C,4.1063604468,1.036019904,-0.2559203493\C,2.8161297718,0.9878422914,0.25731635\H,1. 5621782916,-1.5576484155,-1.6152265051\H,3.8666999442,-1.452577228,-2. 5514460258\H,4.8197730888,1.7530564708,0.1253138975\H,2.5169964125,1.6 536465393,1.0566991977\C,-0.6035610113,-0.0740240557,3.7573903967\C,0. 5947272893,-0.0060024403,4.4743711528\C,0.60504416,0.0059681707,5.8663 313032\C,-0.6032549527,-0.0514814158,6.5683236556\C,-1.8105463876,-0.1 214673557,5.860505513\C,-1.8079516391,-0.1328431779,4.4769503427\H,1.5 308266574,0.0338802718,3.9309945942\H,1.5515622497,0.0574550667,6.3891 202641\H,-2.7366534368,-0.165371848,6.4227365302\H,-2.7383797683,-0.18 75981517,3.9255776224\O,5.7511915809,0.0907086434,-1.8016177617\H,-3.9 862337398,-0.1004230666,-2.3081161293\C,6.4214926682,1.2318837454,-2.1 588045864\O,5.9717637171,2.3399356973,-2.0597419634\C,7.7844684923,0.8 685004872,-2.6873517676\H,7.6873897861,0.1991133833,-3.5466609092\H,8. 3127495504,1.7757755596,-2.9767104179\H,8.3507280035,0.3323571169,-1.9 203711904\O,-0.7121370731,-0.0459516414,7.9238319139\C,0.476761614,0.0 241293792,8.6902504525\H,0.1630474146,0.0174483027,9.7351176153\H,1.12 88198171,-0.8381860333,8.5035088941\H,1.0347083649,0.9465725516,8.4865 889787\H,-1.8717366559,0.2841960385,-3.5597217897\\Version=EM64L-G09Re vc.01\state=2-a\hf=-1239.1277284\s2=0.766244\s2-1=0.\s2a=0.75016\rmsd= 6.357e-09\RMSF=1.065e-06\Dipole=1.3281312,-0.4441281,-0.5046797\Quadru pole=3.6843847,-14.7956586,11.1112739,-3.8259815,2.7320898,6.203464\pg =C01 [X(C22H183O3)]\\@ S 79
4x 1\1\GIC-OCTOPUS\FOpt\UB3LYP\6-31G(2d,p)\C21H183O2(2)\PIOTR\25-Mar-20 14\0\\#P B3LYP/6-31G(2d,p) FOpt=tight freq(noraman) SCF=Direct #P Geom =(odistance,oangle) fcheck\\7-h-1,3-(phome)-benzotrazinyl, C1\\0,2\C,-1.8373029912,0.1417124117,-2.4728759568\C,-0.6230827724,0.187491794, -1.7989448436\C,-0.5945104995,0.0207024386,-0.4079774137\C,-1.80580175 03,-0.1418890693,0.3205707182\C,-3.0157322952,-0.1953625463,-0.3956497 55\C,-3.0334965589,-0.0619641073,-1.7739620393\H,0.295007375,0.3606135 015,-2.3444581015\,0.5737236232,0.0327928001,0.3507928806\,-1.820910 5879,-0.2214426109,1.6848891853\H,-3.9259317892,-0.329890714,0.1777354 336\C,-0.6424663388,-0.0780098099,2.2958452065\,0.5542364491,0.051378 7141,1.7113025899\C,1.8814637229,0.0933710138,-0.2153223373\C,2.284851 4472,-0.8237666302,-1.1926734268\C,3.569301388,-0.7705893061,-1.708982 0667\C,4.4793160284,0.1904241901,-1.2493807327\C,4.083817056,1.0945142 257,-0.2587465781\C,2.7890950586,1.0406049415,0.2517706731\H,1.5960715 726,-1.5874725143,-1.5343338893\H,3.8985468796,-1.4767708618,-2.462473 1435\H,4.767957883,1.8430027428,0.1193875078\H,2.4767744763,1.73037366 24,1.0261496753\C,-0.6299171761,-0.0749058213,3.7777344369\C,0.5643027 76,-0.0019067877,4.5008207934\C,0.5681472283,0.0010204485,5.8930458486 \C,-0.6427636601,-0.0711724549,6.5889002859\C,-1.846059853,-0.14578464 44,5.8751259381\C,-1.8369429897,-0.1477237012,4.4913832358\H,1.5023165 752,0.0488280268,3.961667222\H,1.5117982808,0.0563740604,6.4206765018\ H,-2.7744177293,-0.2011867337,6.4326633283\H,-2.7641566376,-0.20631157 8,3.9350245509\O,5.7118542335,0.156498115,-1.8208582117\H,-3.975146963 7,-0.1029341502,-2.3111129043\O,-0.7579709948,-0.0762357339,7.94444699 81\C,0.4267500622,-0.0047781785,8.7165154186\H,0.1085846398,-0.0219607 977,9.759979062\H,1.0856597081,-0.8611822006,8.5261488799\H,0.97990224 93,0.9228775523,8.5232431397\H,-1.8511535054,0.269875818,-3.5499564228 \C,6.6748383344,1.1028356451,-1.3902701627\H,6.3451289628,2.13080663,- 1.5853622654\H,6.8988391943,0.993042913,-0.3219771142\H,7.5766678887,0.8991493066,-1.9689831447\\Version=EM64L-G09RevC.01\State=2-A\HF=-1125.7695796\S2=0.76577\S2-1=0.\S2A=0.750149\RMSD=2.071e-09\RMSF=9.631e-07 \Dipole=1.5792484,0.4980943,-0.3810605\Quadrupole=3.4089438,-9.729674, 6.3207301,5.266,4.0954784,0.0064273\PG=C01 [X(C21H183O2)]\\@ S 80