Oxazines: A New Class Of Second-Order Nonlinear Optical Switches Supporting Information

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1 Oxazines: A New Class Of Second-Order Nonlinear Optical Switches Supporting Information Pierre Beaujean, a Flavie Bondu, b Aurélie Plaquet, a Jaume Garcia-Amorós, c Janet Cusido, c Françisco M. Raymo, c,* Frédéric Castet, b,* Vincent Rodriguez, b,* and Benoît Champagne a,* a University of Namur, Laboratoire de Chimie Théorique, Unité de Chimie Physique Théorique et Structurale, rue de Bruxelles, 61, B-5000 Namur, Belgium b Université de Bordeaux, Institut des Sciences Moléculaires (ISM), UMR 5255 CNRS, Cours de la Libération 351, F Talence Cedex, France c Laboratory for Molecular Photonics, Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, FL , USA c a R 2 M06-2X Table S1. Correlation [ΔE TDDFT = c x ΔE Exp. + a] between experimental maximum absorption energies and TDDFT/M06-2X vertical excitation energies for the lowest-energy band of the UV/vis absorption spectra of compounds 3, 4, 11, and 12 in their closed and protonated open forms. IEF- PCM was used to describe the solvent (chloroform) effects. The G(d) basis set was employed. S1

2 Closed (a) Open (b + ) ΔE (ev) Γ (cm -1 ) F ΔE (ev) Γ (cm -1 ) F Table S2. Characteristics of the main low-energy band of the UV/vis absorption spectra of the closed and protonated open forms in chloroform [Energies of the maximum of absorption (ΔE), full width at half maximum, Γ], and frequency dispersion factor, F = β HRS (1064)/ β HRS (1907). Closed (a) Open (b + ) Open (b) β MP2 (0) β CPHF (0) β TDHF (1907) β MP2 (1907) β MP2 (0) β CPHF (0) β TDHF (1907) β MP2 (1907) β MP2 (0) β CPHF (0) Table S3. First hyperpolarizabilities (a.u.) of the protonated open and closed forms as determined at different levels of approximation within the IEFPCM solvation model (solvent = chloroform) with the G(d) basis set together with the estimates of the MP2 dynamic first hyperpolarizabilities calculated using the multiplicative scheme. The last two columns report the static MP2 and HF first hyperpolarizabilities of the zwitterionic open forms evaluated within the IEFPCM solvation model (solvent = chloroform) and the G(d) basis set. S2

3 S 1 N S 3 O 2 N S 2 OH S 4 R 1 S 5 acid base S 1 S 3 a N S 2 S 4 R 1 O S 5 NO 2 hν S 2 S 1 N S 3 O 2 N O S 4 R 1 S 5 b b + 3a 4a 5a 6a 7a 8a 9a 10a 11a 12a S S S S S R b 5b 6b 7b 8b 9b 10b 11b 12b S S S S S R b+ 4b+ 5b+ 6b+ 7b+ 8b+ 9b+ 10b+ 11b+ 12b+ S S S S S R Table S4. Mulliken charges on the fragments of the oxazine compounds 3-12 in their closed (a) as well as photochemically- (b) and acidly-open (b + ) forms as determined at the IEF-PCM/M06/6-311G(d) level (in chloroform). S3

4 Closed (a) open (b) open (b+) static 1064nm static 1064nm static 1064nm β HRS DR β HRS DR β HRS DR β HRS DR β HRS DR β HRS DR Table S5: Static and dynamic (1064nm) hyper-rayleigh scattering first hyperpolarizabilities (!!"#, a.u.) and depolarization ratios (DR) of the closed and open forms of compounds 1-12, obtained at the IEF-PCM/TDHF/6-311+G(d) level (in chloroform). β HRS (b)/ β HRS (a) Static 1064nm β HRS (b + )/ β HRS (a) Static 1064nm Table S6: Static and dynamic (1064nm) β HRS (open)/ β HRS (closed) contrast ratios for the photo- and acido-triggered opening of compounds 1-12, as determined at the IEF-PCM/TDHF/6-311+G(d) level (in chloroform). S4

5 Normalized absorbance (arb. unit.) nm 446 nm 3a 3b + Normalized absorbance (arb. unit.) nm 421 nm 4a 4b Wavelength (nm) Wavelength (nm) Normalized absorbance (arb. unit.) nm 610 nm 11a 11b + Normalized absorbance (arb. unit.) nm 545 nm 12a 12b Wavelength (nm) Wavelength (nm) Figure S1. Experimental UV/vis absorption spectra of the closed and protonated open forms of 3, 4, 11, and 12 recorded in chloroform. The vertical grey line at 532 nm highlights the SHG signal wavelength. S5

6 50 HRS Intensity (a.u.) Incident Power (a.u.) 5 Calc. Exp. 5.0x x x x x10-3 C X (mol L -1 ) x10 0 Hyper Rayleigh Intensity (arb. unit) Ψ (deg.) ρ = HRS Intensity (a.u.) Incident Power (a.u.) 5 Calc. Exp x x x x10-4 C X (mol L -1 ) Figure S2. Power scan (left) and polarization scan (right) of closed (top) and protonated open (bottom) forms of 3. Hyper Rayleigh Intensity (arb. unit) Ψ (deg.) ρ = 0.87 S6

7 7 HRS Intensity (a.u.) Incident Power (a.u.) 5 Calc. Exp x x x x10-3 C X (mol L -1 ) Hyper Rayleigh Intensity (arb. unit) Ψ (deg.) ρ = HRS Intensity (a.u.) Incident Power (a.u.) 5 Calc. Exp x x x x10-3 C X (mol L -1 ) Figure S3. Power scan (left) and polarization scan (right) of closed (top) and protonated open (bottom) forms of 4. Hyper Rayleigh Intensity (arb. unit) Ψ (deg.) ρ = 0.78 S7

8 18 HRS Intensity (a.u.) Incident Power (a.u.) 5 Calc. Exp. 6.0x x x x10-4 C X (mol L -1 ) x10 0 Hyper Rayleigh Intensity (arb. unit) Ψ (deg.) ρ = HRS Intensity (a.u.) Incident Power (a.u.) 5 Calc. Exp. 1.0x x x x x10-5 C X (mol L -1 ) x10 0 Figure S4. Power scan (left) and polarization scan (right) of closed (top) and protonated open (bottom) forms of 11. Hyper Rayleigh Intensity (arb. unit) Ψ (deg.) ρ = 0.83 S8

9 9 HRS Intensity (a.u.) Incident Power (a.u.) 5 Calc. Exp. 1.0x x x x10-4 C X (mol L -1 ) x10 0 Hyper Rayleigh Intensity (arb. unit) Ψ (deg.) ρ = HRS Intensity (a.u.) Incident Power (a.u.) 5 Calc. Exp. 8.0x x x x10-5 C X (mol L -1 ) x10 0 Figure S5. Power scan (left) and polarization scan (right) of closed (top) and protonated open (bottom) forms of 12. Hyper Rayleigh Intensity (arb. unit) Ψ (deg.) ρ = 0.80 S9

10 Δq = q(b + ) - q(b) S 1 S 2 S 3 S 4 S 5 R Figure S6a. Variations of the Mulliken charges from the zwitterionic to protonated open forms, Δq = q(b + ) q(b) of the oxazines (3-12) as determined at the IEF-PCM/M06/6-311G(d) level (in chloroform). S10

11 Figure S6b Spatial distribution on the S 1 -S 5 and R 1 molecular moieties of the variations of the Hirshfeld charges when opening the oxazine, as determined at the IEF-PCM/M06/6-311G(d) level (in chloroform). Top) photo-triggered opening, Δq = q(b) q(a); middle) acido-triggered opening, Δq = q(b + ) q(a) and bottom) from the photo- to the acido-triggered open forms, Δq = q(b + ) q(b). S11

12 Figure S6c Spatial distribution on the S 1 -S 5 and R 1 molecular moieties of the variations of the NPA (natural population analysis) charges when opening the oxazine, as determined at the IEF- PCM/M06/6-311G(d) level (in chloroform). Top) photo-triggered opening, Δq = q(b) q(a); middle) acido-triggered opening, Δq = q(b + ) q(a) and bottom) from the photo- to the acido-triggered open forms, Δq = q(b + ) q(b). S12

13 Figure S7(1-12).IEF-PCM (solvent= chloroform )/TDDFT/M 06-2X/6-311+G (d)uv/visabsorptionspectraofthe closed(a),photochem icaly open (b),and acidlyopen(b+)form s ofcom pounds 1-12togetherwith details (excitation energies and wavelengths,oscilatorstrengths,and m olecularorbitals involved in the m ajorsingly-excited determ inants)on dom inantlow-energy transitions. Molecule 1 Closed (a) Photochemically open (b) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) HOMO LUMO HOMO LUMO Photochemically open (b) HOMO LUMO HOMO-1 LUMO HOMO-2 LUMO 94.9 Acidly open (b + ) HOMO LUMO HOMO LUMO Acidly open (b + )

14 Molecule 2 Closed (a) Photochemically open (b) Acidly open (b + ) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) { HOMO LUMO HOMO-1 LUMO HOMO-1 LUMO HOMO-1 LUMO { HOMO-2 LUMO+1 HOMO-3 LUMO HOMO-2 LUMO Photochemically open (b) HOMO LUMO HOMO-1 LUMO 83.3 Acidly open (b + ) HOMO LUMO HOMO-1 LUMO HOMO LUMO

15 Molecule 3 Closed (a) Photochemically open (b) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) HOMO-2 LUMO HOMO-1 LUMO Photochemically open (b) HOMO-1 LUMO HOMO LUMO Acidly open (b + ) HOMO LUIMO HOMO-1 LUMO Acidly open (b + )

16 Molecule 4 Closed (a) Photochemically open (b) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) HOMO-2 LUMO HOMO-1 LUMO Photochemically open (b) HOMO-1 LUMO HOMO LUMO Acidly open (b + ) HOMO LUMO HOMO-1 LUMO HOMO-1 LUMO Acidly open (b + )

17 Molecule 5 Closed (a) Photochemically open (b) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) HOMO LUMO HOMO LUMO HOMO-3 LUMO 71.8 Photochemically open (b) HOMO LUMO HOMO-1 LUMO HOMO LUMO Acidly open (b + ) HOMO LUMO HOMO-4 LUMO Acidly open (b + )

18 Molecule 6 Closed (a) Photochemically open (b) Acidly open (b + ) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) HOMO-1 LUMO Photochemically open (b) HOMO-3 LUMO+1 HOMO-3 LUMO HOMO LUMO { Acidly open (b + ) { HOMO-3 LUMO HOMO-1 LUMO HOMO-1 LUMO HOMO LUMO HOMO LUMO HOMO LUMO HOMO-6 LUMO

19 Molecule 7 Closed (a) Photochemically open (b) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) HOMO-1 LUMO { Photochemically open (b) HOMO-3 LUMO+1 HOMO-3 LUMO HOMO LUMO Acidly open (b + ) HOMO LUMO HOMO-4 LUMO HOMO-2 LUMO states of < f < in 7b Acidly open (b + )

20 Molecule 8 Closed (a) Photochemically open (b) Acidly open (b + ) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) HOMO LUMO HOMO-2 LUMO HOMO LUMO Photochemically open (b) { { HOMO-1 LUMO HOMO LUMO HOMO LUMO HOMO-1 LUMO HOMO LUMO Acidly open (b + ) HOMO LUMO HOMO-2 LUMO

21 Molecule 9 Closed (a) Photochemically open (b) Acidly open (b + ) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) { HOMO-2 LUMO HOMO LUMO HOMO-1 LUMO Photochemically open (b) HOMO-1 LUMO HOMO LUMO HOMO-2 LUMO 55.2 Acidly open (b + ) HOMO LUMO HOMO-1 LUMO HOMO-1 LUMO

22 Molecule 10 Closed (a) Photochemically open (b) Acidly open (b + ) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) { HOMO LUMO+1 HOMO-1 LUMO HOMO LUMO HOMO-1 LUMO Photochemically open (b) HOMO-1 LUMO HOMO LUMO Acidly open (b + ) HOMO LUMO HOMO-1 LUMO HOMO-1 LUMO

23 Molecule 11 Closed (a) Photochemically open (b) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) HOMO LUMO HOMO-2 LUMO { Photochemically open (b) HOMO LUMO+7 HOMO LUMO HOMO-1 LUMO HOMO LUMO Acidly open (b + ) HOMO LUMO HOMO-2 LUMO Acidly open (b + )

24 Molecule 12 Closed (a) Photochemically open (b) Acidly open (b + ) Root Energy (ev) Wavelength (nm) f Transition % Closed (a) { HOMO-3 LUMO HOMO LUMO HOMO LUMO HOMO-2 LUMO Photochemically open (b) HOMO-1 LUMO HOMO-2 LUMO HOMO LUMO HOMO-7 LUMO 43.2 Acidly open (b + ) HOMO LUMO HOMO-3 LUMO HOMO-1 LUMO

25 p-nitrophenol p-nitrophenol p-nitrophenolate Root Energy (ev) Wavelength (nm) f Transition % Neutral HOMO LUMO HOMO-3 LUMO HOMO LUMO HOMO-1 LUMO Negatively charged HOMO LUMO HOMO-4 LUMO 91.9

26 Closed (a) 1a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H C H C C C C H C H C H H N C H H H C H H H C H H C H H O C H H H C H H H a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C H H H H C S26

27 C C C C C H C C C H H S N O C H H H C H H H N O C H H H O O a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N S27

28 O O H C H C H C C C H C H H S a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O H C H C H C C C S H C H H S28

29 5a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O H C H C H C C C C H C H C H H N C C C C H C H C H H H C C S29

30 C C H C H C H H H a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O H C C C C H C H C H H H a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C S30

31 C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O H H a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C S31

32 C N O O H C H C H C C C C H C H C H H N C H H H C H H H a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O S32

33 H C H C H C C C C H C H C H H O N O a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O H C H C H C C C C H S33

34 C H C H H C O H a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O H C H C H C C C C H C C C H C C H H O O S34

35 N C H H C H H C H H H C H H H a, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O H C H C H C C C C H C H C S35

36 H C C C C C H C H H H N C H H H Photochemically open (b) 1b, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H C H C C C C H C H C H H N C H H H C H H H C H H C H H O C H H H S36

37 C H H H b, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C H H H H C C C C C C H C C C H H S N O C H H H C H H H N O C H H H O O b, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C S37

38 H H H O C H H C C C H C H C C N O O H C H C H C C C H C H H S b, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C S38

39 N O O H C H C H C C C H H S C H b, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O H C H C H C C C C H C H S39

40 C H H N C C C C H C H C H H H C C C C H C H C H H H b, IEF-PCM(chloroform)/M06/6-311G(d), E= C C C C C C C C H H H H N C H H H C H H H O C H H C C C H C H C C N O O H C S40

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