Synthesis, electrochemical and theoretical studies of V-Shaped donor-acceptor hexaazatriphenylene (HAT) derivatives for second harmonic generation Rafael Juárez a, b, Mar Ramos a, José L. Segura b *, Jesús Orduna c *, Belén Villacampa d, Raquel Alicante d a Departamento de Tecnología Química y Ambiental, Universidad Rey Juan Carlos, C/ Tulipán s/n, Móstoles, 28933, Spain. b Departamento de Química Orgánica I, Universidad Complutense de Madrid. Avda. Complutense s/n, Madrid, 28040, Spain. c Departamento de Química Orgánica, ICMA,Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain, d Departamento de Física de la Materia Condensada, ICMA,Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain segura@quim.ucm.es, jorduna@unizar.es Table of Contents: (1) General experimental and theoretical procedures.s2-s3 (2) ew compounds 1 H and 13 C MR spectra S4-S25 (3) Optimized geometries and energies S26-S33 (4) References S34 S1
General experimental and theoretical procedures All commercial chemicals were purchased and used as received. 1,3,5-trichloro-2,4,6-trinitrobenzene (6), 1 1,3,5-trinitro-2,4,6-triaminebencene (7), 2 hexaaminebenzene (8), 3 pyrazino[2,3-f]quinoxaline-5,6- diamine (9) 4 were synthesized by following previously described synthetic procedures. Solvents were dried using common methods: THF was distilled over a sodium benzophenone mixture. Dichloromethane was distilled over P 2 O 5. Electrochemical measurements were carried out using dry solvents and and degassing the samples bubbling argon for 10 minutes prior to the measure. MR spectra were recorded using solvent signals as internal references (CHCl 3 : 7.26 ppm and 77.0 ppm). The quadratic nonlinear response of compounds 1 4 was measured by the Electric Field Induced Second Harmonic generation (EFISH) technique. The fundamental wavelength at 1.907 µm was generated in a hydrogen Raman cell pumped by the 1.064 µm light from a Q-switched d:yag laser (10 pps, 8 ns/pulse). The vertically polarized fundamental beam was split in two. One of them was focused into a wedge shaped EFISH cell. The other one, acting as a reference beam, excited a PP [- (4-nitrophenyl)-L-prolinol] powder sample whose second harmonic signal is used to correct for laser fluctuations. The voltage applied through the 2 mm separated electrodes of the liquid sample cell was 4.5 kv. The output light from the sample was detected with a photomultiplier, with suitable interference filters to block the fundamental beam out. Computational Procedures: All theoretical calculations were performed by using the Gaussian 09 5 program. The molecular geometries of compounds 1-4 were optimized restricted to C 2 symmetry using the B3P86 6 functional and the 6-31G* basis set. 7 The same model chemistry (B3P86/6-31G*) was used for TD-DFT calculations and the excited state dipole moments were calculated by using the CI density. S2
Molecular hyperpolarizabilities were calculated by the Coupled Perturbed Hartree Fock method (CPHF) using the HF/6-31G* model. The default Gaussian 09 parameters were used in every case. Molecular orbital contours were plotted using Molekel 4.3. 8 S3
OHex 1 OHex S4
OHex 650 600 550 500 450 OHex 1 400 350 300 250 200 150 100 50 0 160 150 140 130 120 110 100 90 80 f1 (ppm) 70 60 50 40 30 20 10 S5
Bu 2 2 Bu 2 S6
Bu 2 2 Bu 2 S7
OHex OHex 3 S8
OHex OHex 3 S9
Bu 2 Bu 2 4 S10
Bu 2 Bu 2 4 S11
CH 2 Br CH 2 Br 11 S12
CH 2 Br CH 2 Br 11 S13
CH 2 PO(OMe) 2 CH 2 PO(OMe) 2 12 S14
CH 2 PO(OMe) 2 CH 2 PO(OMe) 2 12 S15
Si(iPr) 3 OC 6 H 13 17 S16
5500 Si(iPr) 3 5000 4500 4000 OC 6 H 13 17 3500 3000 2500 2000 1500 1000 500 0 160 150 140 130 120 110 100 90 80 f1 (ppm) 70 60 50 40 30 20 10 0 S17
OC 6 H 13 O O OC 6 H 13 21 S18
OC 6 H 13 O O OC 6 H 13 21 S19
Si(iPr) 3 Bu 2 18 S20
Si(iPr) 3 Bu 2 18 S21
1200 Bu 2 1100 O 1000 O 900 Bu 2 800 22 700 600 500 400 300 200 100 0-100 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 f1 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 S22
S23-10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 f1 (ppm) 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 O O Bu 2 Bu 2 22
CHO OC 6 H 13 13 S24
5500 CHO 5000 4500 OC 6 H 13 4000 13 3500 3000 2500 2000 1500 1000 500 0 230 220 210 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0-10 S25
Theoretically optimized geometries (cartesian coordinates) and calculated energies for compounds 1-4 (B3P86/6-31G*) 1: Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) umber umber Type X Y Z --------------------------------------------------------------------- 1 6 0 0.003304 3.397005 6.791976 2 6 0 0.001276 1.436999 5.650500 3 6 0 0.000702 0.730000 6.875785 4 6 0 0.002743 2.694591 8.007369 5 6 0 0.000407 0.706469 4.389319 6 6 0-0.000702-0.730000 6.875785 7 6 0-0.001276-1.436999 5.650500 8 6 0-0.000407-0.706469 4.389319 9 6 0-0.003304-3.397005 6.791976 10 6 0-0.002743-2.694591 8.007369 11 1 0 0.004137 4.485748 6.779435 12 1 0 0.003096 3.225161 8.957917 13 1 0-0.004137-4.485748 6.779435 14 1 0-0.003096-3.225161 8.957917 15 6 0-0.000372 0.720559 2.091411 16 6 0 0.000372-0.720559 2.091411 17 7 0-0.001523-1.374290 8.054856 18 7 0-0.002656-2.782250 5.622867 19 7 0-0.000085-1.388290 3.242994 20 7 0 0.000085 1.388290 3.242994 21 7 0 0.002656 2.782250 5.622867 22 7 0 0.001523 1.374290 8.054856 23 6 0-0.002132 1.510264 0.867668 24 6 0-0.000638 2.860634 0.874837 25 6 0 0.002132-1.510264 0.867668 26 6 0 0.000638-2.860634 0.874837 27 6 0-0.002590 3.746892-0.274746 28 6 0-0.006650 3.299061-1.611216 29 6 0-0.000372 5.132387-0.062791 30 6 0-0.008424 4.187613-2.666249 31 1 0-0.008408 2.234393-1.825546 32 6 0-0.002132 6.042543-1.114228 33 1 0 0.002797 5.506270 0.958118 34 6 0-0.006213 5.571225-2.429266 35 1 0-0.011483 3.842115-3.695189 36 1 0-0.000305 7.105479-0.901721 37 6 0 0.002590-3.746892-0.274746 38 6 0 0.006650-3.299061-1.611216 39 6 0 0.000372-5.132387-0.062791 40 6 0 0.008424-4.187613-2.666249 41 1 0 0.008408-2.234393-1.825546 42 6 0 0.002132-6.042543-1.114228 43 1 0-0.002797-5.506270 0.958118 S26
44 6 0 0.006213-5.571225-2.429266 45 1 0 0.011483-3.842115-3.695189 46 1 0 0.000305-7.105479-0.901721 47 8 0-0.008233 6.354853-3.531931 48 8 0 0.008233-6.354853-3.531931 49 6 0-0.005976 7.765434-3.365121 50 6 0-0.008293 8.391455-4.744786 51 1 0 0.884517 8.072627-2.797224 52 1 0-0.893129 8.075073-2.793286 53 6 0-0.006579 9.917021-4.697684 54 1 0 0.869869 8.030270-5.294498 55 1 0-0.889685 8.032126-5.290546 56 6 0-0.008529 10.551305-6.086027 57 1 0-0.883826 10.270324-4.136596 58 1 0 0.873516 10.268476-4.139916 59 1 0 0.868035 10.197529-6.647806 60 1 0-0.887753 10.199114-6.644623 61 6 0 0.005976-7.765434-3.365121 62 6 0 0.008293-8.391455-4.744786 63 1 0-0.884517-8.072627-2.797224 64 1 0 0.893129-8.075073-2.793286 65 6 0 0.006579-9.917021-4.697684 66 1 0-0.869869-8.030270-5.294498 67 1 0 0.889685-8.032126-5.290546 68 6 0 0.008529-10.551305-6.086027 69 1 0 0.883826-10.270324-4.136596 70 1 0-0.873516-10.268476-4.139916 71 1 0-0.868035-10.197529-6.647806 72 1 0 0.887753-10.199114-6.644623 73 6 0-0.007122 12.077415-6.057463 74 6 0-0.008985 12.699116-7.449293 75 1 0 0.871718 12.428029-5.498788 76 1 0-0.883426 12.429585-5.495786 77 1 0-0.008173 13.793087-7.400495 78 1 0 0.873771 12.390988-8.021630 79 1 0-0.894024 12.392159-8.018721 80 6 0 0.007122-12.077415-6.057463 81 6 0 0.008985-12.699116-7.449293 82 1 0-0.871718-12.428029-5.498788 83 1 0 0.883426-12.429585-5.495786 84 1 0 0.008173-13.793087-7.400495 85 1 0-0.873771-12.390988-8.021630 86 1 0 0.894024-12.392159-8.018721 87 1 0-0.005269 0.975674-0.075479 88 1 0 0.002195 3.339817 1.852834 89 1 0 0.005269-0.975674-0.075479 90 1 0-0.002195-3.339817 1.852834 --------------------------------------------------------------------- SCF Done: E(RB3P86) = -2034.65576788 A.U. S27
2: Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) umber umber Type X Y Z --------------------------------------------------------------------- 1 6 0-0.121355 3.394471 7.082907 2 6 0-0.048483 1.435615 5.940649 3 6 0-0.026382 0.729337 7.166841 4 6 0-0.099332 2.692823 8.298379 5 6 0-0.019196 0.706014 4.679858 6 6 0 0.026382-0.729337 7.166841 7 6 0 0.048483-1.435615 5.940649 8 6 0 0.019196-0.706014 4.679858 9 6 0 0.121355-3.394471 7.082907 10 6 0 0.099332-2.692823 8.298379 11 1 0-0.160441 4.482651 7.070377 12 1 0-0.120868 3.223189 9.248896 13 1 0 0.160441-4.482651 7.070377 14 1 0 0.120868-3.223189 9.248896 15 6 0-0.001900 0.721664 2.381030 16 6 0 0.001900-0.721664 2.381030 17 7 0 0.052126-1.373295 8.345859 18 7 0 0.096428-2.780450 5.913770 19 7 0 0.022442-1.388380 3.533294 20 7 0-0.022442 1.388380 3.533294 21 7 0-0.096428 2.780450 5.913770 22 7 0-0.052126 1.373295 8.345859 23 6 0 0.022339 1.509801 1.158663 24 6 0-0.024175 2.861390 1.167107 25 1 0 0.089920 0.976726 0.216832 26 1 0-0.087666 3.334078 2.146460 27 6 0-0.022339-1.509801 1.158663 28 6 0 0.024175-2.861390 1.167107 29 1 0-0.089920-0.976726 0.216832 30 1 0 0.087666-3.334078 2.146460 31 6 0 0.000785 3.754535 0.028541 32 6 0 0.090047 3.333655-1.310507 33 6 0-0.054187 5.140378 0.240522 34 6 0 0.113410 4.229409-2.360446 35 1 0 0.148067 2.273117-1.539865 36 6 0-0.030607 6.053513-0.799928 37 1 0-0.107732 5.511854 1.261320 38 6 0 0.036330 5.627558-2.144733 39 1 0 0.191713 3.833679-3.365839 40 1 0-0.053904 7.107650-0.554873 41 6 0-0.000785-3.754535 0.028541 42 6 0-0.090047-3.333655-1.310507 43 6 0 0.054187-5.140378 0.240522 44 6 0-0.113410-4.229409-2.360446 45 1 0-0.148067-2.273117-1.539865 46 6 0 0.030607-6.053513-0.799928 47 1 0 0.107732-5.511854 1.261320 48 6 0-0.036330-5.627558-2.144733 49 1 0-0.191713-3.833679-3.365839 S28
50 1 0 0.053904-7.107650-0.554873 51 7 0 0.010186 6.527324-3.196835 52 7 0-0.010186-6.527324-3.196835 53 6 0 0.048483 7.949961-2.876727 54 6 0-0.176426 8.896801-4.048807 55 1 0 0.998470 8.213951-2.379573 56 1 0-0.745347 8.143608-2.145184 57 6 0-0.288508 10.344569-3.572361 58 1 0 0.646324 8.827338-4.772261 59 1 0-1.095569 8.617556-4.581022 60 6 0-0.476945 11.330258-4.719468 61 1 0-1.128984 10.431736-2.870783 62 1 0 0.612611 10.610675-3.003115 63 1 0-0.560119 12.358033-4.351643 64 1 0 0.367815 11.294158-5.417053 65 1 0-1.386084 11.106069-5.289168 66 6 0-0.048483-7.949961-2.876727 67 6 0 0.176426-8.896801-4.048807 68 1 0-0.998470-8.213951-2.379573 69 1 0 0.745347-8.143608-2.145184 70 6 0 0.288508-10.344569-3.572361 71 1 0-0.646324-8.827338-4.772261 72 1 0 1.095569-8.617556-4.581022 73 6 0 0.476945-11.330258-4.719468 74 1 0 1.128984-10.431736-2.870783 75 1 0-0.612611-10.610675-3.003115 76 1 0 0.560119-12.358033-4.351643 77 1 0-0.367815-11.294158-5.417053 78 1 0 1.386084-11.106069-5.289168 79 6 0-0.428614-6.094091-4.520144 80 6 0-1.940280-5.927495-4.686422 81 1 0-0.054706-6.816302-5.249992 82 1 0 0.083362-5.156889-4.762307 83 6 0-2.326846-5.441468-6.080245 84 1 0-2.431834-6.888789-4.480090 85 1 0-2.310741-5.224609-3.928870 86 6 0-3.832410-5.280836-6.258709 87 1 0-1.830083-4.481647-6.280446 88 1 0-1.940720-6.143741-6.832535 89 1 0-4.081000-4.925657-7.264287 90 1 0-4.353169-6.232708-6.103484 91 1 0-4.240448-4.560998-5.540103 92 6 0 0.428614 6.094091-4.520144 93 6 0 1.940280 5.927495-4.686422 94 1 0 0.054706 6.816302-5.249992 95 1 0-0.083362 5.156889-4.762307 96 6 0 2.326846 5.441468-6.080245 97 1 0 2.431834 6.888789-4.480090 98 1 0 2.310741 5.224609-3.928870 99 6 0 3.832410 5.280836-6.258709 100 1 0 1.830083 4.481647-6.280446 101 1 0 1.940720 6.143741-6.832535 102 1 0 4.081000 4.925657-7.264287 103 1 0 4.353169 6.232708-6.103484 104 1 0 4.240448 4.560998-5.540103 --------------------------------------------------------------------- SCF Done: E(RB3P86) = -2152.76059848 A.U. S29
3: Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) umber umber Type X Y Z --------------------------------------------------------------------- 1 6 0-0.337476 3.379765 7.916217 2 6 0-0.139332 1.429031 6.777677 3 6 0-0.072772 0.725866 8.002366 4 6 0-0.271238 2.680777 9.132636 5 6 0-0.062851 0.703765 5.515265 6 6 0 0.072772-0.725866 8.002366 7 6 0 0.139332-1.429031 6.777677 8 6 0 0.062851-0.703765 5.515265 9 6 0 0.337476-3.379765 7.916217 10 6 0 0.271238-2.680777 9.132636 11 1 0-0.445774 4.462959 7.902173 12 1 0-0.327002 3.209269 10.082692 13 1 0 0.445774-4.462959 7.902173 14 1 0 0.327002-3.209269 10.082692 15 6 0-0.043525 0.718698 3.232800 16 6 0 0.043525-0.718698 3.232800 17 7 0 0.140077-1.367524 9.181511 18 7 0 0.272844-2.767199 6.748448 19 7 0 0.106934-1.400167 4.371373 20 7 0-0.106934 1.400167 4.371373 21 7 0-0.272844 2.767199 6.748448 22 7 0-0.140077 1.367524 9.181511 23 6 0-0.048562 1.434829 2.011026 24 6 0-0.029250 2.031233 0.950759 25 6 0 0.048562-1.434829 2.011026 26 6 0 0.029250-2.031233 0.950759 27 6 0 0.000336 2.716606-0.287836 28 6 0 0.417139 2.057756-1.462263 29 6 0-0.380700 4.063702-0.378417 30 6 0 0.444034 2.721324-2.672378 31 1 0 0.728229 1.019376-1.404045 32 6 0-0.358563 4.736296-1.593539 33 1 0-0.699745 4.583429 0.519424 34 6 0 0.053777 4.066129-2.750697 35 1 0 0.766463 2.223430-3.581101 36 1 0-0.661146 5.776467-1.630347 37 6 0-0.000336-2.716606-0.287836 38 6 0-0.417139-2.057756-1.462263 39 6 0 0.380700-4.063702-0.378417 40 6 0-0.444034-2.721324-2.672378 41 1 0-0.728229-1.019376-1.404045 42 6 0 0.358563-4.736296-1.593539 43 1 0 0.699745-4.583429 0.519424 44 6 0-0.053777-4.066129-2.750697 45 1 0-0.766463-2.223430-3.581101 46 1 0 0.661146-5.776467-1.630347 47 8 0 0.112171 4.622016-3.981035 48 8 0-0.112171-4.622016-3.981035 49 6 0-0.271238 5.981738-4.138067 50 6 0-0.117453 6.334830-5.603300 S30
51 1 0 0.365274 6.623204-3.511373 52 1 0-1.312508 6.116072-3.810654 53 6 0-0.508843 7.779457-5.903482 54 1 0 0.923984 6.157156-5.898949 55 1 0-0.733765 5.646620-6.195126 56 6 0-0.354181 8.138684-7.378827 57 1 0-1.550317 7.951710-5.595749 58 1 0 0.104794 8.461897-5.297788 59 1 0 0.687120 7.966267-7.686873 60 1 0-0.965977 7.455077-7.985056 61 6 0 0.271238-5.981738-4.138067 62 6 0 0.117453-6.334830-5.603300 63 1 0-0.365274-6.623204-3.511373 64 1 0 1.312508-6.116072-3.810654 65 6 0 0.508843-7.779457-5.903482 66 1 0-0.923984-6.157156-5.898949 67 1 0 0.733765-5.646620-6.195126 68 6 0 0.354181-8.138684-7.378827 69 1 0 1.550317-7.951710-5.595749 70 1 0-0.104794-8.461897-5.297788 71 1 0-0.687120-7.966267-7.686873 72 1 0 0.965977-7.455077-7.985056 73 6 0-0.742617 9.580108-7.697825 74 6 0-0.582615 9.926593-9.173723 75 1 0-0.131264 10.262358-7.091117 76 1 0-1.783454 9.750891-7.390130 77 1 0-0.863696 10.965589-9.375086 78 1 0 0.455118 9.792919-9.500759 79 1 0-1.211045 9.284186-9.801516 80 6 0 0.742617-9.580108-7.697825 81 6 0 0.582615-9.926593-9.173723 82 1 0 0.131264-10.262358-7.091117 83 1 0 1.783454-9.750891-7.390130 84 1 0 0.863696-10.965589-9.375086 85 1 0-0.455118-9.792919-9.500759 86 1 0 1.211045-9.284186-9.801516 --------------------------------------------------------------------- SCF Done: E(RB3P86) = -2032.06327579 A.U. S31
4: Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) umber umber Type X Y Z --------------------------------------------------------------------- 1 6 0-0.336091 3.379508 8.007393 2 6 0-0.138977 1.428626 6.867818 3 6 0-0.072496 0.725776 8.093327 4 6 0-0.269986 2.680924 9.223715 5 6 0-0.062963 0.703600 5.605534 6 6 0 0.072496-0.725776 8.093327 7 6 0 0.138977-1.428626 6.867818 8 6 0 0.062963-0.703600 5.605534 9 6 0 0.336091-3.379508 8.007393 10 6 0 0.269986-2.680924 9.223715 11 1 0-0.443990 4.462868 7.993377 12 1 0-0.325372 3.209492 10.173839 13 1 0 0.443990-4.462868 7.993377 14 1 0 0.325372-3.209492 10.173839 15 6 0-0.043601 0.719619 3.321967 16 6 0 0.043601-0.719619 3.321967 17 7 0 0.139319-1.367502 9.272426 18 7 0 0.271964-2.767168 6.839468 19 7 0 0.107338-1.400397 4.461648 20 7 0-0.107338 1.400397 4.461648 21 7 0-0.271964 2.767168 6.839468 22 7 0-0.139319 1.367502 9.272426 23 6 0-0.049101 1.437204 2.103166 24 6 0-0.027873 2.045268 1.048285 25 6 0 0.049101-1.437204 2.103166 26 6 0 0.027873-2.045268 1.048285 27 6 0-0.000271 2.760677-0.169564 28 6 0 0.372810 2.141626-1.373934 29 6 0-0.327100 4.127709-0.220452 30 6 0 0.406507 2.841386-2.566503 31 1 0 0.659645 1.094258-1.361780 32 6 0-0.299167 4.831901-1.407963 33 1 0-0.604149 4.637486 0.697143 34 6 0 0.050320 4.209210-2.630309 35 1 0 0.727851 2.314057-3.455550 36 1 0-0.553936 5.884059-1.379487 37 6 0 0.000271-2.760677-0.169564 38 6 0-0.372810-2.141626-1.373934 39 6 0 0.327100-4.127709-0.220452 40 6 0-0.406507-2.841386-2.566503 41 1 0-0.659645-1.094258-1.361780 42 6 0 0.299167-4.831901-1.407963 43 1 0 0.604149-4.637486 0.697143 44 6 0-0.050320-4.209210-2.630309 45 1 0-0.727851-2.314057-3.455550 46 1 0 0.553936-5.884059-1.379487 47 7 0 0.031312 4.896520-3.829725 48 7 0-0.031312-4.896520-3.829725 49 6 0-0.031312 6.349236-3.824254 S32
50 6 0 1.283224 7.042727-3.462196 51 1 0-0.826290 6.664139-3.140139 52 1 0-0.362344 6.679681-4.811529 53 6 0 1.151658 8.562680-3.426640 54 1 0 1.630666 6.674971-2.487942 55 1 0 2.053897 6.755094-4.191292 56 6 0 2.459650 9.265161-3.080345 57 1 0 0.788516 8.921268-4.400178 58 1 0 0.380651 8.842522-2.695209 59 1 0 2.336284 10.352934-3.058122 60 1 0 2.828194 8.951065-2.097243 61 1 0 3.239882 9.033242-3.814455 62 6 0 0.031312-6.349236-3.824254 63 6 0-1.283224-7.042727-3.462196 64 1 0 0.826290-6.664139-3.140139 65 1 0 0.362344-6.679681-4.811529 66 6 0-1.151658-8.562680-3.426640 67 1 0-1.630666-6.674971-2.487942 68 1 0-2.053897-6.755094-4.191292 69 6 0-2.459650-9.265161-3.080345 70 1 0-0.788516-8.921268-4.400178 71 1 0-0.380651-8.842522-2.695209 72 1 0-2.336284-10.352934-3.058122 73 1 0-2.828194-8.951065-2.097243 74 1 0-3.239882-9.033242-3.814455 75 6 0-0.526695-4.212562-5.019832 76 6 0-0.317890-4.946606-6.338493 77 1 0 0.000347-3.253299-5.094303 78 1 0-1.597977-3.969611-4.911569 79 6 0-0.734775-4.076988-7.524017 80 1 0 0.738890-5.224797-6.446787 81 1 0-0.898278-5.878005-6.363371 82 6 0-0.575407-4.789557-8.861959 83 1 0-1.780178-3.764812-7.395842 84 1 0-0.138631-3.154425-7.525121 85 1 0-0.875434-4.145112-9.694558 86 1 0 0.465570-5.088203-9.030587 87 1 0-1.190645-5.695612-8.904480 88 6 0 0.526695 4.212562-5.019832 89 6 0 0.317890 4.946606-6.338493 90 1 0-0.000347 3.253299-5.094303 91 1 0 1.597977 3.969611-4.911569 92 6 0 0.734775 4.076988-7.524017 93 1 0-0.738890 5.224797-6.446787 94 1 0 0.898278 5.878005-6.363371 95 6 0 0.575407 4.789557-8.861959 96 1 0 1.780178 3.764812-7.395842 97 1 0 0.138631 3.154425-7.525121 98 1 0 0.875434 4.145112-9.694558 99 1 0-0.465570 5.088203-9.030587 100 1 0 1.190645 5.695612-8.904480 --------------------------------------------------------------------- SCF Done: E(RB3P86) = -2150.16871457 A.U. S33
References (1) Hill, M.; Taylor, J. F. J. Org. Chem. 1960, 25, 1037-1038. (2) Kohne, B.; Praefcke, K. Liebigs Ann. Chem. 1985, 522-528. (3) Rogers, D. Z. J. Org. Chem. 1986, 51, 3904-3905. (4) Moucheron, C.; Mesmaeker, A. K. D.; Choua, S. Inorg. Chem. 1997, 36, 584-592. (5) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; akatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; akajima, T.; Honda, Y.; Kitao, O.; akai, H.; Vreven, T.; Montgomery, J. J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K..; Staroverov, V..; Kobayashi, R.; ormand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega,.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.; Gaussian, Inc.: Wallingford CT, 2009. (6) The B3P86 Functional consists of Becke s three parameter hybrid functional (Becke, A. D., J. Chem. Phys. 1993, 5648-5652) with the nonlocal correlation provided by the Perdew 86 expression (Perdew,J. P. Phys. Rev. B 1986, 8822-8824). (7) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213-222. (8) Portmann, S.; thi, H. P. Chimia 2000, 54, 766-770. S34