Alkyl-functionalization of 3,5-bis(2-pyridyl)-1,2,4,6- thiatriazine

Μέγεθος: px

Εμφάνιση ξεκινά από τη σελίδα:

Download "Alkyl-functionalization of 3,5-bis(2-pyridyl)-1,2,4,6- thiatriazine"

Σατάν Διδασκάλου
5 χρόνια πριν
Προβολές:

1 Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016 Electronic Supporting Information Alkyl-functionalization of 3,5-bis(2-pyridyl)-1,2,4,6- thiatriazine Elizabeth Kleisath, a,b Nathan J. Yutronkie, a,b Ilia Korobkov, a Bulat M. Gabidullin a and Jaclyn L. Brusso *,a,b a Department of Chemistry and Biomolecular Science and b Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada. Contents (23 pages) Page S2 Page S15 Page S18 Page S23 NMR Spectra Crystallography UV-Vis and Computational Studies References S1

2 ppm Figure S1. 1 H NMR spectrum of 12 in MeCN-d3. S2

3 ppm Figure S2. 1 H NMR spectrum of 13 in MeCN-d3. S3

4 ppm Figure S3. 1 H NMR spectrum of [3,5-bis(N-methyl-2-pyridinium)-S-methyl-1,2,4,6- thiatriazine][otf]2 in MeCN-d3. S4

5 ppm Figure S4. 1 H NMR spectrum of 14 in MeCN-d3. S5

6 ppm Figure S5. 1 H NMR spectrum of 15 in MeCN-d3. S6

7 ppm Figure S6. 1 H NMR spectrum of 17 in MeCN-d3. S7

8 ppm Figure S7. 1 H NMR spectrum of 18 in MeCN-d3. S8

9 ppm Figure S8. 13 C NMR spectrum of 12 in MeCN-d3. S9

10 ppm Figure S9. 13 C NMR spectrum of 13 in MeCN-d3. S10

11 ppm Figure S C NMR spectrum of 14 in MeCN-d3. S11

12 ppm Figure S C NMR spectrum of 15 in MeCN-d3. S12

13 ppm Figure S C NMR spectrum of 17 in MeCN-d3. S13

14 ppm Figure S C NMR spectrum of 18 in MeCN-d3. S14

15 Table S1. Crystallographic data and selected collection parameters for 12, 14, [3,5-bis(N-methyl- 2-pyridinium)-S-methyl-1,2,4,6-thiatriazine][OTf]2 ([(MePy)2MeTTA][OTf]2) and 17. Parameters [(MePy)2MeTTA][OTf]2 17 Empirical formula C14H14BF4N5S C14H13N5S C17H17F6N5O6S3 C14H13IN5NaS Formula weight Crystal system orthorhombic orthorhombic triclinic triclinic Space group P P P 1 P 1 a (Å) (2) 5.799(3) 8.938(4) (3) b (Å) (2) (9) (5) (3) c (Å) (4) (10) (5) (3) α (deg) (19) (8) β (deg) (18) (8) γ (deg) (17) (9) V (Å3) (6) (14) (8) (4) Z Dcalc (mg/m3) T (K) 200(2) 258(2) 200(2) 200(2) μ (mm -1 ) θ range for data to to to to collection (deg) no. of total reflections no. of unique reflections Rint R1, WR2 (on F2) , , , , S15

16 Table S2. Bond length comparisons of the central TTA ring for compounds 12, 14, [3,5-bis(Nmethyl-2-pyridinium)-S-methyl-1,2,4,6-thiatriazine][OTf]2 ([(MePy)2MeTTA][OTf]2) and 17, as well as other previously reported TTA derivatives [3,5-bis(N-hydro-2-pyrinium)-Sbromo-1,2,4,6-thiatriazine][Br][Br3] ([(HPy)2BrTTA][Br][Br3]), 1 3,5-bis(pyridyl)-4-hydro- S-oxo-1,2,4,6-thiatriazine (Py2TTAH=O) 1 and Py2TTAH (11). 2 Bond numbers are in reference to the numbers shown in the schematic, and all lengths are reported in Angstroms (Å). Aromatic [(MePy) 2MeTTA] [OTf] 2 R2=Me, R3=Me [(HPy) 2BrTTA] [Br][Br 3] R2=Br, R3=Br Anti-Aromatic 14 R2=Et 17 R1=Na-I, 12 R1=H, 11 R1=H Py2TTAH=O R1=H, R2=Et R2=Et R2=O (31) (20) (26) (47) (37) 1.279(2) (43) (32) (17) (17) (52) (31) 1.396(2) (42) (35) (23) (21) (56) (38) 1.391(2) (42) (31) (22) (26) (48) (37) 1.278(2) (43) (23) (13) (12) (38) (22) 1.693(2) (27) (23) (18) (19) (42) (25) 1.692(2) (28) S16

this ring adopts a shallow boatlike arrangement. Figure S15.

bis(n-methyl-2-pyridinium)-s-methyl-1,2,4,6-thiatriazine][otf]2.

17 Figure S14. Calculated twist angles between planes of the thiatriazine and pyridine rings of 14. The central plane was calculated without the S and N3 atoms, as this ring adopts a shallow boatlike arrangement. Figure S15. Calculated twist angles between planes of the thiatriazine and pyridine rings of [3,5- bis(n-methyl-2-pyridinium)-s-methyl-1,2,4,6-thiatriazine][otf]2. The central plane was calculated without the S11 and N22 atoms, as this ring adopts a shallow boat-like arrangement. Hydrogens removed for clarity (left). S17

18 Table S3: Frontier molecular orbitals and corresponding energies (in ev) for 14, 15, and 11. Energies were calculated at the B3LYP/6-311+G(2d,p) level of theory, and orbital probability diagrams were generated using GaussView 5.0 software LUMO LUMO LUMO HOMO HOMO HOMO S18

19 Table S4 TD DFT optical transitions a for 14 and 15, calculated at the B3LYP/6-311+G(2d,p) level of theory on geometry optimized structures with Gaussian 09 software. 3 k E (ev) f E (ev) f a k = order of excitation energy and ƒ = oscillator strength. S19

20 Table S5 Selected TD DFT transitions for 14. Transitions shown are those with the greatest calculated oscillator strength, as well as the HOMO to LUMO transition. Calculations were performed at the B3LYP/6-311+G(2d,p) level of theory with acetonitrile solvation using Gaussian 09 software. 3 Calculated λ (nm) Transitions Oscillator Strength (f) 394 HOMO LUMO HOMO-6 LUMO HOMO-5 LUMO HOMO-4 LUMO HOMO-3 LUMO HOMO-2 LUMO HOMO-1 LUMO HOMO LUMO+1 HOMO-6 LUMO HOMO-5 LUMO HOMO-4 LUMO HOMO-3 LUMO HOMO-2 LUMO HOMO-1 LUMO HOMO LUMO+2 HOMO-8 LUMO HOMO-5 LUMO+1 HOMO-4 LUMO+1 HOMO-2 LUMO+1 HOMO LUMO+4 HOMO-8 LUMO HOMO-5 LUMO+1 HOMO-4 LUMO+1 HOMO-2 LUMO+1 HOMO LUMO S20

21 Table S6 Selected TD DFT transitions for 15. Transitions shown are those with the greatest calculated oscillator strength, as well as the HOMO to LUMO transition. Calculations were performed at the B3LYP/6-311+G(2d,p) level of theory with acetonitrile solvation using Gaussian 09 software. 3 Calculated λ (nm) Transitions Oscillator Strength (f) 385 HOMO LUMO HOMO-6 LUMO HOMO-4 LUMO+1 HOMO-3 LUMO HOMO-2 LUMO+1 HOMO-5 LUMO HOMO-3 LUMO HOMO-1 LUMO HOMO-5 LUMO HOMO-4 LUMO HOMO-2 LUMO HOMO LUMO+2 HOMO-8 LUMO HOMO-5 LUMO+1 HOMO-4 LUMO+1 HOMO-2 LUMO S21

22 Table S7 Comparative table for the measured molar coefficients of extinction a with the corresponding calculated oscillator strengths b for 14 and λ (nm) ε (μm -1 cm -1 ) Calculated λ (nm) a Optical measurements were performed on dilute MeCN solutions. b TD DFT/B3LYP/6-311+G(2d,p) level of theory on geometry optimized structures where f = oscillator strength using Gaussian 09 software. 3 f S22

23 References 1. A. A. Leitch, I. Korobkov, A. Assoud and J. L. Brusso, Chemical Communications, 2014, 50, N. J. Yutronkie, A. A. Leitch, I. Korobkov and J. L. Brusso, Crystal Growth & Design, 2015, 15, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. J. A. Montgomery, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox, Gaussian 09, Revision A.02; Gaussian, Inc.: Wallingford, CT, S23

Σχετικά έγγραφα

Structural Expression of Exo-Anomeric Effect

Supporting Information for Structural Expression of Exo-Anomeric Effect Elena R. Alonso, Isabel Peña, Carlos Cabezas, and José L. Alonso* Contents Table S1: Transition frequencies of conformer cc-β- 4