Singlet Photoreactivity of 3-Methyl-2-phenyl-2Hazirine

Transcription

1 /CH16604_AC CSIRO 2017 Australian Journal of Chemistry 2017, 70(4), SUPPLEMENTARY MATERIAL Singlet Photoreactivity of 3-Methyl-2-phenyl-2Hazirine Geethika K. Weragoda,a Anushree Das, a Sujan K. Sarkar, a H. Dushanee M. Sriyarathne, a Xiaoming Zhang, a Bruce S. Ault, a Anna D. Gudmundsdottir* a a Department of Chemistry, University of Cincinnati, PO Box , Cincinnati, Ohio , USA *Corresponding author. Anna.Gudmundsdottir@uc.edu Table of Content 1. Calculations Optimization of TD-DFT of Optimized T1 of Optimization of Ylide TD-DFT of the Ylide Calculated Transition State for azirine 1 forming ylide Calculated transition state for ylide 6 forming Optimized indole Calculated Transition State for 9 forming isoindole Optimized Isoindole Irradiation of azirine 1 with 254 nm and above 300 nm light Figure S1. Irradiation of azirine 1 in argon matrix with light at 254 nm and above 300 nm Figure S2. Light emission from the UV pen without filter that absorbs visible light Spectra of (2-azidoprop-1-en-1-yl)benzene and Azirine H- and 13C-NMR spectra of (2-azidoprop-1-en-1-yl)benzene IR spectrum of (2-azidoprop-1-en-1-yl)benzene H- and 13C-NMR of Azirine IR Spectrum of Azirine S1

2 1. Calculations 1.1. Optimization of 1 B3LYP 6-31+G(d) Energy = a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z TD-DFT of 1 TD-DFT calculations for azirine 1 gas phase Excitation energies and oscillator strengths: Excited State 1: Singlet-A ev nm f= > > > > > Excited State 2: Singlet-A ev nm f= S2

3 34 -> > > > Excited State 3: Singlet-A ev nm f= > > > > > Excited State 4: Singlet-A ev nm f= > > > > TD-DFT in Methanol (PCM) Excitation energies and oscillator strengths: Excited State 1: Singlet-A ev nm f= > > > > Excited State 2: Singlet-A ev nm f= > > > > Excited State 3: Singlet-A ev nm f= > > > > > Excited State 4: Singlet-A ev nm f= > > > > > Excited State 5: Singlet-A ev nm f= > > TD-DFT in Acetonitrile (PCM) Excitation energies and oscillator strengths: Excited State 1: Singlet-A ev nm f= > > S3

4 35 -> > Excited State 2: Singlet-A ev nm f= > > > > Excited State 3: Singlet-A ev nm f= > > > > > Excited State 4: Singlet-A ev nm f= > > > > > Excited State 5: Singlet-A ev nm f= > > Excited State 6: Singlet-A ev nm f= > > > > > > Optimized T1 of 1 B3LYP/6-31+G(d)E = a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S4

5 Optimization of Ylide 6 B3LYP 6-31+G(d) E = a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S5

6 1.5. TD-DFT of the Ylide 6 TD-DFT in gas phase Excitation energies and oscillator strengths: Excited State 1: Singlet-A ev nm f= > > Excited State 2: Singlet-A ev nm f= > > Excited State 3: Singlet-A ev nm f= > > > Excited State 4: Singlet-A ev nm f= > > Excited State 5: Singlet-A ev nm f= > > > Excited State 6: Singlet-A ev nm f= > > > > > Excited State 7: Singlet-A ev nm f= > > > > > > Excited State 8: Singlet-A ev nm f= > > > > Excited State 9: Singlet-A ev nm f= > > Excited State 10: Singlet-A ev nm f= > > > > > > > > Excited State 11: Singlet-A ev nm f= > > > S6

7 Excited State 12: Singlet-A ev nm f= > > > TD-DFT in Acetonitrile (PCM) Excited State 1: Singlet-A ev nm f= > Excited State 2: Singlet-A ev nm f= > > Excited State 3: Singlet-A ev nm f= > > > Excited State 4: Singlet-A ev nm f= > > Excited State 5: Singlet-A ev nm f= > > > Excited State 6: Singlet-A ev nm f= > > > Excited State 7: Singlet-A ev nm f= > > > > > Excited State 8: Singlet-A ev nm f= > > > > Excited State 9: Singlet-A ev nm f= > > > > > > Excited State 10: Singlet-A ev nm f= > > > > Excited State 11: Singlet-A ev nm f= > > Excited State 12: Singlet-A ev nm f= S7

8 1.6. Calculated Transition State for azirine 1 forming ylide 6. B3LYP/6-31G+(d)Energy = a.u. Negative Frequency: 381 cm -1 (56) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S8

9 1.7 Calculated transition state for ylide 6 forming 9 B3LYP/6-31G+(d) Energy = a.u. Negative Frequency -377 cm -1 (21) Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S9

10 1.8. Optimized indole 9 B3LYP/6-31G+(d) Energy = a.u. Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S10

11 1.9. Calculated Transition State for 9 forming isoindole 10 B3LYP/6-31G+(d)Energy = a.u. Negative frequency (202) cm -1 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S11

12 1.10. Optimized Isoindole 10 B3LYP/6-31G+(d) Energy = Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S12

13 2. Irradiation of azirine 1 with 254 nm and above 300 nm light 0.00 hours of irradiation 1.33 " 4.33 " Wavenumbers [cm -1 ] Figure S1. Irradiation of azirine 1 in argon matrix with light at 254 nm and above 300 nm S13

14 Figure S2. Light emission from the UV pen without filter that absorbs visible light S14

15 3. Spectra of (2-azidoprop-1-en-1-yl)benzene and Azirine H- and 13 C-NMR spectra of (2-azidoprop-1-en-1-yl)benzene S15

16 %R cm IR spectrum of (2-azidoprop-1-en-1-yl)benzene S16

17 H- and 13 C-NMR of Azirine 1 S17

18 %R cm IR Spectrum of Azirine 1 S18