Redox Noninnocence of the Bridge in Copper(II) Salophen and bis-oxamato Complexes

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1 Electronic supplementary Information for Redox Noninnocence of the Bridge in Copper(II) Salophen and bis-oxamato Complexes David de Bellefeuille, a Maylis Orio, b Anne-Laure Barra, c Ally Aukauloo, d,e Yves Journaux, d,f Christian Philouze, g Xavier Ottenwaelder*,a and Fabrice Thomas*,g a. Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec H4B 1R6, Canada. b. Laboratoire de Spectrochimie Infrarouge et Raman, Université des Sciences et Technologies de Lille, UMR CNRS 8516, Villeneuve d Ascq Cedex, France. Present adress : Institut des Sciences Moleculaires de Marseille, Aix Marseille Université, CNRS, Centrale Marseille, ISM2 UMR 7313, Avenue Escadrille Normandie-Niemen, Marseille Cedex 20, France. c. Laboratoire National des Champs Magnétiques Intenses, CNRS, 25 rue des Martyrs, Grenoble, France. d. Institut de Chimie Moléculaire et des Matériaux d Orsay, UMR CNRS 8182, Université Paris-Sud Orsay, France. e. Service de Bioénergétique, Biologie Structurale et Mécanismes (SB2SM), CEA, ibitec-s; Biochimie Biophysique et Biologie Structurale (B3S), I2BC, UMR 9198, Gif-sur-Yvette, France. f. Sorbonne Universités, UPMC Université Paris 06, UMR CNRS 8232, Institut Parisien de Chimie Moléculaire, France. g. Equipe CIRE, Département de Chimie Moléculaire, UMR CNRS 5250, Université Grenoble Alpes, Grenoble Cedex 9, France. S1

2 Tables Table S1. Crystallographic Data for H 2 L 1, Et 2 H 2 L 2, 1 and (PPh 4 )2. H 2 L 1 Et 2 H 2 L 2 1 (PPh 4 ) 2 2 CCDC number Empirical formula C 40 H 58 N 4 O 2 C 36 H 52 N 8 O 12 C 40 H 56 CuN 4 O 2 C 62 H 54 CuN 4 O 6 P 2 Formula weight Temperature 150(2) K 150(2) K 200 K 149(2) K Wavelength Å Å Å Å Crystal system Monoclinic Triclinic Monoclinic Monoclinic Space group P2 1 /n P-1 C2/c P2 1 /n a (8) Å (8) Å (5) Å (11) Å b (12) Å (9) Å (3) Å (2) Å c (12) Å (12) Å (2) Å (11) Å α (10) β (10) (10) (3) (10) γ (10) Volume (4) Å (2) Å (13) Å (7) Å 3 Z Density (calculated) g cm g cm g cm g cm 3 Absorption coefficient F(000) Crystal size mm Index ranges h = 15 15, k = 22 2, l = mm h = 14 14, k = 16 16, l = mm h = 28 28, k = 18 18, l = Reflections collected Independent reflections Parameters Goodness of fit Final R indices [I > 2σ(I)] R 1 = 4.98%, wr 2 = 10.65% R indices (all data) R 1 = 9.51%, wr 2 = 12.72% Largest diff. peak and hole and e Å 3 R 1 = 3.87%, wr 2 = 9.47% R 1 = 4.82%, wr 2 = 10.08% and e Å 3 R 1 = 3.96%, wr 2 = 8.34% R 1 = 6.48%, wr 2 = 9.01% and e Å mm h = 19 18, k = 34 35, l = R 1 = 3.87%, wr 2 = 8.63% R 1 = 6.34%, wr 2 = 9.66% and e Å 3 S2

3 Numbering used in the tables: Table S2. Selected calculated bond lengths (Å) for H 2 L 1, (H 2 L 1 ) +, 1, triplet 1 + and doublet Bond H 2 L 1 (H 2 L 1 ) + 1 1H Cu-O Cu-O Cu-N Cu-N C9-O C9-C C10-C C11-C C12-C C13-C C9-C C8-C C7-N N1-C C1-C C2-C C3-C C4-C C5-C C6-C C3-N S3

4 Table S3. Selected calculated bond lengths (Å) for Et 2 H 2 L 2, (Et 2 H 2 L 2 ) +, 2 2 and triplet 2. Bond Et 2 H 2 L 2 (Et 2 H 2 L 2 ) Cu-O Cu-N C8-O C8-C C7-N N1-C C1-C C2-C C3-C C4-C C5-C C6-C C4-N Table S4. Spin Hamiltonian parameters for the oxidized proligands. [a] Calculated Experimental Species g 1 g 2 g 3 g iso A N A H g iso A N A H (H 2 L 1 ) (Et 2 H 2 L 2 ) [a] Hyperfine constants in MHz (divide by 1.39 g to convert into gauss). A N for 2 equivalent 14 N. A H for 12 equivalent 1 H. S4

5 Table S5. Geometric analysis of the central ring in 1, doublet 1 + and doublet Sum of angles about N º º º Sum of angles about C º 360º 359.9º Sum of angles about C º º 359.8º Distances to N1-C1-C2-C3 plane C1, C2, C3, N1 within: Å Å Å N2 at: Å Å Å Distances to C1-N1-C2-C6 plane C1, C2, C3, C6, N1 within: Å Å Å N2 at: Å Å Å Angle between C1-C2-C3 and C4-C5-C6 planes 2.82º 6.63º 14.41º Angle between C1-N1-C2-C6 and C3-N2-C2-C4 planes 3.90º 11.90º 26.08º Table S6. Geometric analysis of the central ring in 2 2, triplet 2 and doublet Sum of angles about N º º º Sum of angles about C º 360º º Sum of angles about C º º 359.8º Distances to N1-C1-C2-C3 plane C1, C2, C3, N1 within: Å Å Å N2 at: Å Å Å Distances to C1-N1-C2-C6 plane C1, C2, C3, C6, N1 within: N2 at: Angle between C1-C2-C3 and C4-C5-C6 planes 1.34º 4.83º 11.30º Angle between C1-N1-C2-C6 and C3-N2-C2-C4 planes 1.74º 9.12º 23.89º S5

6 Table S7. Contribution to the ZFS in triplet species 1 + and 2. a D (cm 1 ) E / D D (cm 1 ) E / D SS SOC Total a SS and SOC stand for spin-spin and spin-orbit interactions, total incorporates both contributions. S6

7 Figures: Figure S1. ORTEP representation at 50% ellipsoid probability of the proligands. H atoms are omitted for clarity, except those engaged in hydrogen bonding. (a) H 2 L 1 ; (b) one molecule in Et 2 H 2 L 2. Figure S2. Cyclovoltammogram of 1 mm CH 2 Cl 2 solutions (+ 0.1 M nbu 4 NClO 4 ) of proligands H 2 L 1 (a) and Et 2 H 2 L 2 (b). Potentials are relative to the Fc + /Fc redox couple. Scan rates: 0.1 V / s, T = 298 K. S7

8 25 20 (a) 12 (b) 15 8 / mm -1 cm / mm -1 cm / nm / nm Figure S3. UV-Vis spectra of proligands and their electrochemically oxidized products. (a) (H 2 L 1 ) (black) and (H 2 L 1 ) + (red), (b) Et 2 H 2 L 2 (black) and (Et 2 H 2 L 2 ) + (red) in CH 2 Cl 2 (+0.1 M nbu 4 ClO 4 ), T = 298 K (neutral species) or 233 K (cations). Figure S4. Evolution of the UV-Vis spectrum of H 2 L 1 in CH 2 Cl 2 solution upon addition of 0-1 molar equivalent of acetylferrocenium triflate. T = 233 K. S8

9 Figure S5. Evolution of the UV-Vis spectrum of Et 2 H 2 L 2 in CH 2 Cl 2 solution upon addition of 0-1 molar equivalent of of acetylferrocenium triflate. T = 233 K. (a) (b) d '' db d '' db B / mt B / mt Figure S6. Isotropic solution X-Band EPR spectra at T = 298 K of: (a) (H 2 L 1 ) + and (b) (Et 2 H 2 L 2 ) + generated by electrolysis at 233 K (1 mm in CH 2 Cl 2, 0.1 M nbu 4 ClO 4 ). Conditions: (a) Microwave Freq GHz, power: 8 mw, Mod Freq. 100 khz, Amp. 0.1 mt; (b) Microwave Freq GHz, power: 8 mw, Mod Freq. 100 khz, Amp. 0.3 mt. S9

10 Color scheme: Cu: orange, O: red; N: dark blue; C: green; H: white. Figure S7. DFT-optimized structure of H 2 L 1 and selected bond lengths. Figure S8. DFT-optimized structure of (H 2 L 1 ) + and selected bond lengths. S10

11 Figure S9. DFT-optimized structure of Et 2 H 2 L 2 and selected bond lengths. Figure S10. DFT-optimized structure of (Et 2 H 2 L 2 ) + and selected bond lengths. S11

12 Figure S11. Localized SOMOs for (H 2 L 1 ) +. Figure S12. Localized SOMOs for (Et 2 H 2 L 2 ) / mm -1 cm / nm Figure S13. Evolution of the UV-Vis spectrum of 1 in CH 2 Cl 2 solution upon addition of 0-1 molar equivalent of HClO 4. T = 298 K. S12

13 Figure S14. X-band EPR spectrum of 2 2 in 1 mm CH 2 Cl 2 frozen solution (+0.1 M nbu 4 ClO 4 ). Microwave Freq GHz, power: 5 mw, Mod. Freq. 100 khz, Amp: 0.3 mt. T = 9 K. Solid lines: experimental spectrum, dotted lines: simulation using the parameters given in the text. I / A E / V Figure S15. CV curve of a 1 mm CH 2 Cl 2 solution (+0.1 M nbu 4 NPF 6 ) of 1. Potentials are referenced to the Fc + /Fc redox couple. Scan rate: 100 mv/s, T = 298 K. S13

14 Figure S16. X-band EPR spectra of: 2 2 (a, black) and 2 (b, red) immediately after electrolysis at 233 K (1 mm in CH 2 Cl 2, 0.1 M nbu 4 ClO 4 ). Microwave Freq GHz power: 8 mw, Mod. Freq. 100 KHz, Amp: 0.3 mt. T = 9 K. Figure S17. DFT-optimized structure of 1 and selected bond lengths. S14

15 Figure S18. DFT-optimized structure of 1H + and selected bond lengths. Figure S19. DFT-optimized structure of triplet 1 + and selected bond lengths. S15

16 Figure S20. DFT-optimized structure of doublet 1 2+ and selected bond lengths. Figure S21. DFT-optimized structure of 2 2 and selected bond lengths. S16

17 Figure S22. DFT-optimized structure of triplet 2 and selected bond lengths. Figure S23. Side views of the central rings in the calculated structures of: (a) 1, (b) triplet 1 +, (c) doublet 1 2+, (d) 2 2, (e) triplet 2, (f) doublet 2. S17

18 Figure S24. Localized SOMOs for: (a) doublet 1, (b) triplet 1 + and (c) doublet Figure S25. Localized SOMOs for: (a) doublet 2 2 and (b) triplet 2 Figure S26. TD-DFT assignment of the UV-Vis bands for doublet 1. S18

19 Figure S27. TD-DFT assignment of the UV-Vis bands for doublet S19

20 Figure S28. TD-DFT assignment of the UV-Vis bands for doublet Figure S29. FTIR spectra of (PPh 4 ) 2 2 2H 2 O (top), (PPh 4 ) 2 x H 2 O (middle) and ferrocene (bottom). S20

21 [benzaldehyde] d '' db B / T Figure S30. Powder EPR spectra of [PPh 4 ]2 at 331 GHz. T = 10 K. Solid lines: Experimental spectra ; Dotted lines: Simulations for a mononuclear (S = ½) species (green, g // = 2.181, A // = 21 mt for a copper nucleus, g _ _ = 2.035) and triplet species (red, D = 0.11 cm 1, E/D = 0, g = 2.039) Time / h Figure S31. Aerobic oxidation of benzyl alcohol by 1. [benzyl alcohol] = 2 M in CH 2 Cl 2, [tbuok] = 20 mm, [2 2 ] = 1 mm, T = 293 K. Black squares: PhCH 2 OH, red circles: PhCD 2 OD. S21

22 a) d '' db b) c) d) B / mt Figure S32. Spin trapping experiments using PBN. [benzyl alcohol] = 5 M in CH 2 Cl 2, [tbuok] = 20 mm, [1] = 0.6 mm, T = 293 K. The spectra were recorded in the multiscan mode (10 scans) after 10 min (a and c) and 1h40 (b and d) reaction time at 293 K. a,b) With complex 1; c,d) Blank without complex. a) d '' db b) c) d) B / mt Figure S33. Spin trapping experiments using PBN. [benzyl alcohol] = 5 M in CH 2 Cl 2, [tbuok] = 20 mm, [2 2 ] = 0.6 mm, T = 293 K. The spectra were recorded in the multiscan mode (10 scans) after 10 min (a and c) and 1h40 (b and d) reaction time at 293 K. a,b) With complex 2 2 ; c,d) Blank without complex. S22

23 d '' db B / mt Figure S34. Spin trapping experiments using PBN. [benzyl alcohol] = 5 M in CH 2 Cl 2, [tbuok] = 20 mm, [2 2 ] = 0.6 mm, T = 293 K. The spectrum was recorded in the multiscan mode (10 scans) after 10 min reaction time at 293 K. Black line: Experimental spectrum; Red line: Simulation using the parameters given in the text. a) d '' db b) B / mt Figure S35. Spin trapping experiment using PBN (larger spectral window showing the copper signal). [benzyl alcohol] = 5 M in CH 2 Cl 2, [tbuok] = 20 mm, [Complex] = 0.6 mm, T = 293 K. The spectra were recorded in the multiscan mode (10 scans) after 1h40 reaction time at 293 K. a) 1; b) 2 2. S23