ESI. for. Substitution Pattern on Anthrol Carbaldehydes: Excited State Intramolecular Proton

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1 Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the Owner Societies 2017 ESI for Substitution Pattern on Anthrol Carbaldehydes: Excited State Intramolecular Proton Transfer (ESIPT) with a Lack of Phototautomer Fluorescence Sermsiri Chaiwongwattana, Đani Škalamera, Nađa Došlić, * Cornelia Bohne, ǁ and Nikola Basarić * Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, Thailand Department of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, Croatia. Fax: ; nbasaric@irb.hr Department of Physical Chemistry, Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, Croatia. Fax: ; nadja.doslic@irb.hr ǁ Department of Chemistry, University of Victoria, Box 1700 STN CSC, Victoria BC, V8W 2Y2, Canada. Table of contents: 1. Synthetic reaction schemes and procedures S2 2. Calculations (Tables S1-S5 and Fig. S1-S13) S4 3. UV-vis and fluorescence spectra of 1-5 (Table S6- S8 and Fig. S14-S31) S13 4. Quantum yields of fluorescence S24 5. Calculated state energy diagrams for 1-3 (Fig S32-S35) S25 6. LFP data (Fig. S36-S49) S27 7. Optimized molecular structure coordinates for 1-3 (Tables S9-S32) S33 8. NMR spectra S51 9. References S61 S1

2 1. Synthetic reaction schemes Carbaldehyde 1 was synthesized by a known route 1 starting from the commercialy available tetralin. In the first step tetralin reacted with succinanhydride under Friedel-Crafts conditions to give keto-acid 6, 2 and then, the keto group was reduced in a Clemensen reaction. 3 The tricyclic threecyclic system was obtained in a cyclization with CH 3 SO 3 H catalyst, 4 where 8 is formed under kinetic control in high yield and purity if the reaction is conducted for a short time. Compound 8 in the presence of a strong base (NaH) gave carbanion which reacted with ethyl formate to give product 9 in 81% yield. 5,6 Finnally, aromatization of the policyclic skeleton was carried out with in situ generated trityl cation giving target carbaldehyde 1 in 87% yield (Scheme S1). 2 O O O O Zn-Hg HCl 1 Scheme S1. OH AlBr 3 benzene CHO Ph 3 COH TFA 6 O COOH CHOH 99% NaH, HCOOEt CH 3 SO 3 H DME 9 cat. EtOH % O COOH Compound 2 was synthesized from 2-anthrol (10), prepared by NaBH 4 reduction 7 of 2- hydroxyanthraquinone (Scheme S2). 8 In an electrophilic aromatic substitution with dichloromethoxymethane 2-anthrol (10) was transformed to a mixture of carbaldehydes 2 and 11, where the desired carbaldehyde 2 was the main product isolated in 35% yield. S2

3 OH CHCl 2OMe SnCl 4 CH 2 Cl 2 / 0 C CHO OH + CHO OH Scheme S2. Compounds 3-5 were prepared from 3-bromo-2-hydroxyanthraquinone (9) according to literature precedent. 7 Antraquinone 9 was subjected to a reduction with NaBH 4 in alkaline aqueous solution (1M Na 2 CO 3 ) to yield pure 2-bromo-3-anthrol (14). In the next step, 14 was treated with excess of BuLi and the lithiated compound reacted with DMF to afford the corresponding aldehyde 3 (Scheme S3). Treatment of antraquinone 9 with an excess of MeLi or PheLi followed by reduction gave methylated anthrol derivative 13-Me or phenyl derivative 13-Ph. Compounds 13 in a reaction with BuLi and quenching with DMF afforded carbaldehydes 4 or OH Br NaBH 4 Na 2 CO 3 /H 2 O O O 12 OH Br 1) RLi OH 2) SnCl 2 /HCl (R=Me) or HI/Et 2 O (R=Ph) R R 13-Me R = CH 3 13-Ph R = Ph Br 1) BuLi / Et 2 O 1) BuLi / Et 2 O 2) DMF 3) H + 2) DMF 3) H + OH R OH 3 CHO R CHO 4 R = CH 3 5 R = Ph Scheme S3. S3

4 2. Calculations 1A 1B 1C 1D 2A 2B 2C 2D 3A 3B 3C 3D Fig S1. Ground state minimum energy structuress of the relevant conformers of 1-3. S4

5 Table S1. ADC(2)-/aug-cc-pVDZ energy barriers in ev for conformational changes as obtained from linearly interpolated path between optimized ground (S 0 ) and excited (S 1 ) state structures. Conformational change S 0 (ev) S 1 (ev) 2B(S 0min ) 2D(S 0min ) 3A(S 0min ) 3B(S 0min ) 3B(S 0min ) 3D(S 0min ) 3B(S 1min ) 3D(S 1min ) 3D(S 1min ) 3B(S 1min ) _ 0.33 _ 0.09 Fig S2. Linearly interpolated path between S 0 (red) optimized structures 3B and 3D showing the barriers for the conformational change in the S 0, S 1 (blue) and S 2 (green) states. S5

6 Table S2. Vertical excitation energies to the three lowest excited states of 1, oscillator strengths (in parenthesis) and the most relevant molecular orbitals involved in the excitation. The computations were performed at the ADC(2)/aug-cc-pVDZ level. S (0.092) S ( ) S (0.026) 1A 1B 1C 1D E (ev) MO E (ev) MO E (ev) MO E (ev) MO L a (ππ*) H L nπ* H-5 L ππ* H-1 L (0.108) 3.53 ( ) 3.72 (0.027) L a (ππ*) H L nπ* H-5 L ππ* H L (0.079) 3.27 ( ) 3.65 (0.017) L a (ππ*) H L nπ* H-4 L ππ* H L (0.096) 3.39 ( ) 3.66 (0.025) L a (ππ*) H L nπ* H-4 L ππ* H L+7 Table S3. Vertical excitation energies to the three lowest excited states of 2, oscillator strengths (in parenthesis) and the most relevant molecular orbitals involved in the excitation. The computations were performed at the ADC(2)/aug-cc-pVDZ level S (0.104) S ( ) S (0.084) 2A 2B 2C 2D E (ev) MO E (ev) MO E (ev) MO E (ev) MO L a (ππ*) H L nπ* H-5 L L b (ππ*) H-1 L 3.19 ( ) 3.22 (0.098) 3.75 (0.037) nπ* H-3 L+1 L a (ππ*) H L+1 L b (ππ*) H-1 L (0.113) 3.34 ( ) 3.70 (0.076) L a (ππ*) H L nπ* H-5 L L b (ππ*) H-1 L 3.12 (0.106) 3.19 ( ) 3.71 (0.053) L a (ππ*) H L+1 nπ* H-4 L+1 L b (ππ*) H-2 L+1 Table S4 Adiabatic excitation energies and vertical emission energies of 1 The computations were performed at the ADC(2)/aug-cc-pVDZ level 1A 1B 1C 1D E a (ev) E emission (ev) S6

7 Table S5 Adiabatic excitation energies and vertical emission energies of 2 The computations were performed at the ADC(2)/aug-cc-pVDZ level 2A 2B 2C 2D E a (ev) E emission (ev) HOMO-5 HOMO LUMO LUMO+8 Fig S3. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 1A computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level. S7

8 HOMO-5 HOMO LUMO LUMO+7 HOMO-4 HOMO LUMO LUMO+8 Fig S4. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 1B computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level Fig S5. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 1C computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level S8

9 HOMO-4 HOMO LUMO LUMO+7 HOMO-5 HOMO-1 HOMO LUMO Fig S6. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 1D computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level Fig S7. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 2A computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level. S9

10 HOMO-3 HOMO-1 HOMO LUMO+1 HOMO-5 HOMO-1 HOMO LUMO Fig S8. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 2B computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level. Fig S9. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 2C computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level. S10

11 HOMO-4 HOMO-1 HOMO LUMO+1 HOMO-5 HOMO-1 HOMO LUMO Fig S10. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 2D computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level. Fig S11. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 3B computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level. S11

12 HOMO-5 HOMO-1 HOMO LUMO HOMO-5 HOMO-1 HOMO LUMO Fig S12. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 3C computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level. Fig S13. Relevant molecular orbitals contributing to the S 1, S 2 and S 3 transitions of 3D computed at the geometry of vertical excitation. The computation were performed at the ADC(2)/aug-cc- pvdz level. S12

13 3. UV-vis and fluorescence spectra of 1-5 Table S6. Spectral properties of 1-5 Cyclohexane a or EtOAc b / nm c 1 447, 422, 403, 362, 344, 328, 296, 264 a 2 441, 434, 416, 394, 358, 341, 325, 300, 289, 274, 255 a 3 458, 363, 345, 329 a 452, 362, 344, 328 b / nm d CH 3 CN / nm c 460,486, (sh), 419, 362, 344, 325, 296, , 449, 472, (sh), 414, 358, - e 341, 298, 272, , 362, 344, 327, 515 b , 374, 355, 338, , 371, 353, 336, / nm d a Spectra measured in cyclohexane. b Spectra measured in EtOAc. c Maxima in the absorption spectra. d Maxima in the fluorescence spectra. e Fluorescence was not detected S13

14 ε / M -1 cm x x x10 4 ε / M -1 cm x x x x OH-2-CHO 2-OH-1-CHO 2-OH-3-CHO 2-OH-3-CHO CH 3 2-OH-3-CHO Ph OH-2-CHO 2-OH-1-CHO 2-OH-3-CHO 2-OH-3-CHO CH 3 2-OH-3-CHO Ph Fig S14. Absorption spectra of 1-5 in CH 3 CN. 5x10 4 4x10 4 OH CHO ε / M -1 cm -1 3x10 4 2x10 4 1x Fig S15. Absorption spectrum of 1 in CH 3 CN. S14

15 Normalized Fluorescence Intensity λ em = 500 nm λ ex = 420 nm Normalized Fluorescence Intensity λ em = 530 nm λ ex = 420 nm Fig S16. Normalized excitation and emission spectra for 1 in cyclohexane (left) and CH 3 CN (right). Relative Fluorescence Intensity 20 oc 24 0C 33 oc 42 oc 51 oc Φ 0 /Φ x x x x10-3 1/T / K -1 Fig S17. Fluorescence spectra of 1 in CH 3 CN (λ ex = 420 nm) at different temperatures. S15

16 1.0x ε / M -1 cm x x x x10 4 ε / M -1 cm CHO OH Fig S18. Absorption spectrum of 2 in CH 3 CN. Normalized Fluorescence Intensity λ em = 500 nm λ ex = 420 nm Normalized Fluorescence Intensity λ em = 530 nm λ ex = 420 nm Fig S19. Normalized excitation and emission spectra for 2 right in cyclohexane(left) and CH 3 CN (right). Relative Fluorescence Intensity 20 oc 24 0C 33 oc 42 oc 51 oc Φ 0 /Φ x x x x10-3 1/T / K -1 Fig S20. Fluorescence spectra of 2 in CH 3 CN (λ ex = 420 nm) at different temperatures. S16

17 60000 O H 6000 CH O ε / M -1 cm Molar Absorption Coefficient Fig S21. Absorption spectrum of 3 in CH 3 CN. Absorbance cyclohexane EtOAc CH 3 CN Relative Fluorescence Intensity EtOAc CH 3 CN Fig S22. Normalized absorption spectra (left) and emission spectra (right) of 3 in different solvents. Relative Fluorescence Intensity λ em = 500 nm λ em = 530 nm λ em = 600 nm Fig S23. Normalized excitation spectra of 3 in CH 3 CN detected at different wavelengths. S17

18 Relative Fluorescence Intensity 20 oc 30 oc 38 oc 47 oc 55 oc Relative Fluorescence Intensity 20 oc 30 oc 38 oc 47 oc 55 oc Fig S24. Normalized excitation spectra of 3 taken in CH 3 CN at different temperatures by detecting emission at 530 nm (left) or 600 nm (right). 70 Relative Fluorescence Intensity c(h 2 O) = 0 M c(h 2 O) = 1.4 M Φ 0 /Φ c(h 2 O) / M Fig S25. Normalized fluorescence spectra of 3 in CH 3 CN at different H 2 O concentration (left), and the corresponding Stern-Volmer plot (right). S18

19 6x10 4 5x10 4 CH 3 ε / M -1 cm -1 4x10 4 3x10 4 2x10 4 CH 3 OH CHO 1x Fig S26. Absorption spectrum of 4 in CH 3 CN. Normalized Fluorescence Intensity λ em = 550 nm λ ex = 450 nm Fig S27. Normalized excitation and emission spectra of 4 in CH 3 CN. S19

20 Relative Fluorescence Intensity oc 25 oc 32 oc 42 oc 51 oc Φ 0 /Φ x x x x10-3 1/T / K -1 Fig S28. Fluorescence spectra of 4 in CH 3 CN (λ ex = 450 nm) at different temperatures. 6x10 4 ε / M -1 cm -1 5x10 4 4x10 4 3x10 4 2x10 4 1x OH CHO Fig S29. Absorption spectrum of 5 in CH 3 CN. S20

21 Normalized Fluorescence Intensity λ em = 550 nm λ ex = 450 nm Fig S30. Normalized excitation and emission spectra of 5 in CH 3 CN. Relative Fluorescence Intensity oc 32 oc 42 oc 51 oc Φ 0 /Φ x x x10-3 1/T / K -1 Fig S31. Fluorescence spectra of 5 in CH 3 CN (λ ex = 450 nm) at different temperatures. Table S7. Calculated absorption and emission maxima for 1-3 in CH 3 CN. / nm / nm calculated / nm / nm calculated b (sh), (3.07 ev) (2.47 ev, 1A) (sh), (3.17 ev) (2.47 ev, 2A) (2.73 ev) (2.29 ev, 3B) 498 (2.49 ev, 3D) a Lowest energy absorption band. b Emissive conformer. S21

22 Fluorescence decays, collected over 1023 time channels, were obtained on an Edinburgh Instruments OB920 single photon counter using a pulsed laser diode for excitation at 405 nm. Obtained histograms were fit as sums of exponentials using global Gaussian-weighted non-linear least-squares fitting based on Marquardt-Levenberg minimization implemented in the Fast software package from Edinburgh Instruments. For decays collected at different wavelengths the lifetimes were linked in the global analysis of the fluorescence decays. Fluorescence decays were fit to a sum of exponentials using the following expression: = exp + exp + exp + (S1) S22

23 Table S8. Lifetimes and pre-exponential factors obtained from the global analysis from the fluorescence decays for 1-5. Molecule/solvent τ / ns a 1/cyclohexane ±0.1 Pre-exponential factors b 500 nm 505 nm 530 nm 550 nm 575 nm /CH 3 CN c 3.9 ± / cyclohexane ± /CH 3 CN d 7.0 ± /EtOAc 3.1± ± (520 nm) (540 nm) 3/CH 3 CN 23.8 ± (520 nm) (540 nm) 4/CH 3 CN 11.8 ± ± /CH 3 CN 0.3 ± ± (580 nm) a The quoted errors correspond to the maximum absolute deviations. The measurements were performed at 20 C. b Estimated errors on pre-exponential factors range from 5% for the main decay components up to 50% for the minor decay components. S23

24 4. Quantum yields of fluorescence and Arrhenius equation The following equation was used for the determination of fluorescence quantum yields: Φ= Φ wherein!! " # " # $ (S2) Φ - quantum yield of fluorescence Φ R - quantum yield of fluorescence of reference compound, acridine yellow in methanol I - intensity of fluorescence (integral of the corrected emission spectrum) I R - intensity of fluorescence (integral of the corrected emission spectrum) for the reference compound A - absorbance of the solution at the excitation wavelength A R - absorbance of the solution of the reference compound at the excitation wavelength n D - refractive index of the solvent (acetonitrile, cyclohexane or ethyl acetate) n D R - refractive index of the solvent use to dissolve the reference compound (methanol) Arrhenius equation was used for the estimation of energy barrier for the population of emissive conformers 3B-3D. %=& exp ' ( )* (S3) ln%=-.&+ ' / )* (S4) wherein k - reaction rate constant E a - activation energy A - pre-exponential factor R - gas constant (8.314 JK -1 mol -1 ) T - absolute temperature S24

25 5. Calculated state energy diagrams for 1-3 Fig S32. State energy diagram for 1A including the relevant singlet and triplet states in the region from S min 0 to S min 1. Fig S33. State energy diagram for 2A including the relevant singlet and triplet states in the region from S min 0 to S min 1. S25

26 Fig S34. State energy diagram for 3D including the relevant singlet and triplet states in the region from S min 0 to S min 1. Fig S35. Energy profiles (in ev) of the electronic ground state (S 0, blue), the La(ππ*) (red) and Lb(ππ*) (green) singlet statess and the two corresponding triplet states (thin lines) of 3A. The energy profiles were obtained by linear interpolation in internal coordinates between the FC and CI geometries. The length of the intramolecular hydrogen bond is given in Å. S26

27 6. LFP data 0.25 A µs 1.4 µs 4.6 µs 8.0 µs A ns 60 ns 100 ns 310 ns Fig S36. Transient absorption spectra of 1 in optically matched (A 355 = 0.35) N 2 -purged (left) and O 2 -purged (right) CH 3 CN solution. Due to the detector saturation by fluorescence the intensity of the negative signal at λ>500 nm is not realistic A ns 60 ns 100 ns 310 ns A H 3 CN O nm CH 3 CN-H 2 O O nm CH 3 CN-H 2 O O nm Time / ns Fig S37. Transient absorption spectra of 1 in O 2 -purged CH 3 CN-H 2 O solution (5:1) (left), and selected decays for N 2 -and O 2 -purged CH 3 CN or CH 3 CN-H 2 O solution of 1 (right). Due to the detector saturation by fluorescence, the intensity of the negative signal at λ>500 nm is not realistic. S27

28 µs 0.6 µs 2.8 µs 7.3 µs 0.0 A A ns 60 ns 110 ns 310 ns Fig S38. Transient absorption spectra of 2 in optically matched (A 355 = 0.35) N 2 -purged (left) and O 2 -purged (right) CH 3 CN solution. Due to the detector saturation by fluorescence, the intensity of the negative signal at λ>500 nm is not realistic A ns 60 ns 110 ns 310 ns A CH 3 CN N nm CH 3 CN O nm CH 3 CN-H 2 O O nm CH 3 CN-H 2 O O nm Time / ns Fig S39. Transient absorption spectra of 2 in O 2 -purged CH 3 CN-H 2 O solution (5:1) (left) and selected decays for N 2 -and O 2 -purged CH 3 CN or CH 3 CN-H 2 O solution of 2 (right). Due to the detector saturation by fluorescence the intensity of the negative signal at λ>500 nm is not realistic. S28

29 ns 240 ns 680 ns 1.6 µs ns 120 ns 200 ns 670 ns 0.00 A 0.00 A Fig S40. Transient absorption spectra of 3 in N 2 -purged (left) and O 2 -purged CH 3 CN (right), obtained by exciting at 355 nm. Due to the detector saturation by fluorescence, the intensity of the negative signal at λ>500 nm is not realistic ns 40 ns 70 ns 120 ns A Fig S41. Transient absorption spectra of 3 in O 2 -purged CH 3 CN obtained by exciting at 266 nm. Due to the detector saturation by fluorescence, the intensity of the negative signal at λ>500 nm is not realistic. S29

30 0.020 A ns 100 ns 180 ns 350 ns Fig S42. Transient absorption spectra of 3 in O 2 -purged CH 3 CN-H 2 O (1:1) obtained by exciting at 355 nm ns 80 ns 180 ns 340 ns A Fig S43. Transient absorption spectra of 3 in O 2 -purged CH 3 CN-D 2 O (1:1), obtained by exciting at 355 nm A H 2 O D 2 O Normalized A H 2 O D 2 O Time / ns Time / ns Fig S44. Decays of the transient absorption of 3 at 380 nm for O 2 -purged CH 3 CN-H 2 O and CH 3 CN-D 2 O solution. The solutions were optically matched at the excitation wavelength (A 355 = 0.35). S30

31 A ns 60 ns 110 ns 320 ns A ns 50 ns 110 ns 320 ns Fig. S45. Transient absorption spectra of 4 in optically matched (A 355 = 0.35) N 2 -purged (left) and O 2 -purged (right) CH 3 CN solution. Due to the detector saturation by fluorescence, the intensity of the negative signal at λ>500 nm is not realistic CH 3 CN CH 3 CN-H 2 O A ns 50 ns 110 ns 320 ns A Fig. S46. Transient absorption spectra of 4 in O 2 -purged CH 3 CN-H 2 O (5:1) solution (left), and transient absorption spectra of 4 in optically matched (A 355 = 0.35) O 2 -purged CH 3 CN and CH 3 CN-H 2 O (5:1) solution with the delay of 50 ns (right) A ns 60 ns 130 ns 320 ns Fig. S47. Transient absorption spectra of 5 in N 2 -purged CH 3 CN solution. Due to the detector saturation by fluorescence, the intensity of the negative signal at λ>500 nm is not realistic. S31

32 A ns 70 ns 120 ns 320 ns A ns 50 ns 90 ns 320 ns Fig S48. Transient absorption spectra of 5 in optically matched (A 355 = 0.35) O 2 -purged CH 3 CN (left) and CH 3 CN-H 2 O (5:1) solution (right). Due to the detector saturation by fluorescence the intensity of the negative signal is not realistic CH 3 CN CH 3 CN-H 2 O A Fig S49. Transient absorption spectra of 5 in optically matched (A 355 = 0.35) O 2 -purged CH 3 CN and CH 3 CN-H 2 O (5:1) solution with the delay of 50 ns (right). S32

33 6. Optimized molecular structure coordinates for 1-3 Table S9. Optimized geometry of 1A in the S 0 state (MP2/aug-cc-pVDZ). C C C C C C C C C C C C C C C H H H H H H H H H H O O Table S10. Optimized geometry of 1B in the S 0 state, MP2/aug-cc-pVDZ. C C C C C C C S33

34 C C C C C C C C H H H H H H H H H H O O Table S11. Optimized geometry of 1C in the S 0 state, MP2/aug-cc-pVDZ. C C C C C C C C C C C C C C C H H S34

35 H H H H H H H H O O Table S12. Optimized geometry of 1D in the S 0 state, MP2/aug-cc-pVDZ. C C C C C C C C C C C C C C C H H H H H H H H H H O O S35

36 Table S13. Optimized geometry of 2A in the S 0 state, MP2/aug-cc-pVDZ. C C C C C C C C C C C C C C C H H H H H H H H H H O O Table S14. Optimized geometry of 2B in the S 0 state, MP2/aug-cc-pVDZ. C C C C C C C C S36

37 C C C C C C C H H H H H H H H H H O O Table S15. Optimized geometry of 2C in the S 0 state, MP2/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H S37

38 H H H H H H H O O Table S16. Optimized geometry of 2D in the S 0 state, MP2/aug-cc-pVDZ. C C C C C C C C C C C C C C C H H H H H H H H H H O O S38

39 Table S17. Optimized geometry of 3A in the S 0 state, MP2/aug-cc-pVDZ. C C C C C C C C C C C C C C C H H H H H H H H H H O O Table S18. Optimized geometry of 3B in the S 0 state, MP2/aug-cc-pVDZ. C C C C C C C C S39

40 C C C C C C C H H H H H H H H H H O O Table S19. Optimized geometry of 3C in the S 0 state, MP2/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H S40

41 H H H H H H H O O Table S20. Optimized geometry of 3D in the S 0 state, MP2/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H H H H H H H H O O S41

42 Table S21. Optimized geometry of 1A in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H H H H H H H H O O Table S22. Optimized geometry of 1B in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C S42

43 C C C C C C C C H H H H H H H H H H O O Table S23. Optimized geometry of 1C in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C C C C C C C C H H S43

44 H H H H H H H H O O Table S24. Optimized geometry of 1D in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H H H H H H H H O O S44

45 Table S25. Optimized geometry of 2A in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H H H H H H H H O O Table S26. Optimized geometry of 2B in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C S45

46 C C C C C C C H H H H H H H H H H O O Table S27. Optimized geometry of 2C in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H S46

47 H H H H H H H O O Table S28. Optimized geometry of 2D in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H H H H H H H H O O S47

48 Table S29. Geometry of 3A S 1 /S 0 CI, ADC(2)/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H H H H H H H H O O Table S30. Optimized geometry of 3B in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C S48

49 C C C C C C C H H H H H H H H H H O O Table S31. Optimized geometry of 3C in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H S49

50 H H H H H H H O O Table S32. Optimized geometry of 3D in the S 1 state, ADC(2)/aug-cc-pVDZ C C C C C C C C C C C C C C C H H H H H H H H H H O O S50

51 7. NMR spectra 1 H NMR (CDCl 3, 300 MHz) spectra of 4-oxo-4-(5,6,7,8-tetrahydronaphthalen-2-yl)butanoic acid (6). O COOH S51

52 1 H NMR (CDCl 3, 600 MHz) of 4-(5,6,7,8-tetrahydronaphthalen-2-yl)butanoic acid (7). COOH S52

53 1 H NMR (CDCl 3, 300 MHz) spectra of 3,4,5,6,7,8-hexahydroanthracen-1(2H)-one (8). O S53

54 1 H NMR (CDCl 3, 300 MHz) spectra of 2-(hydroxymethylene)-3,4,5,6,7,8-hexahydroanthracen-1(2H)-one (9). O CHOH S54

55 1 H NMR (CDCl 3, 600 MHz) spectra of 1-hydroxyanthracene-2-carbaldehyde (1). OH CHO S55

56 1 H NMR (CDCl 3, 600 MHz) spectra of 2-anthrol (10). OH SpinWorks 4: Skalamera DS-2-OH-Ac PPM S56

57 1 H NMR (CDCl 3, 600 MHz) and 13 C NMR (CDCl 3, 600 MHz) spectra of 2-Hydroxyanthracene-1-carbaldehyde (2). CHO OH SpinWorks 4: D. Skalamera DS PPM S57

58 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectra of 3-hydroxyanthracene-2-carbaldehyde (3) OH CHO S58

59 1 H NMR (300 MHz, CDCl 3 ) and 13 C NMR (75 MHz, CDCl 3 ) spectra of 9,10-dimethyl-2-hydroxyanthracene-3-carbaldehyde (4). CH 3 OH CHO CH S59

60 1 H NMR (600 MHz, CDCl 3 ) and 13 C NMR (150 MHz, CDCl 3 ) spectra of 9,10-diphenyl-2-hydroxyanthracene-3-carbaldehyde (5). Ph OH Ph CHO S60

61 9. References 1 C. Biliger, P. Demerseman, R. Royer, J. Heterocycl. Chem., 1985, 22, M. S. Newman, H. V. Zahm, J. Am. Chem. Soc., 1943, 65, E. L. Martin, J. Am. Chem. Soc., 1936, 58, Z. Zhang, R. Sangaiah, A. Gold, L. M. Ball, Org. Biomol. Chem., 2011, 9, A. W. Burgstahler, E. Mosettig, J. Am. Chem. Soc., 1959, 81, E. J. Corey, D. E. Cane, J. Org. Chem., 1971, 36, Đ. Škalamera, K. Mlinarić-Majerski, I. Martin Kleiner, M. Kralj, P. Wan, C. Bohne, N. Basarić, J. Org. Chem., 2017, 82, E. Rochlin, Z. Rappoport, J. Org. Chem., 2003, 68, S61