Supporting Information

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1 Supporting Information Aluminum Complexes of N 2 O 2 3 Formazanate Ligands Supported by Phosphine Oxide Donors Ryan R. Maar, Amir Rabiee Kenaree, Ruizhong Zhang, Yichen Tao, Benjamin D. Katzman, Viktor N. Staroverov, Zhifeng Ding, Joe B. Gilroy* Department of Chemistry and The Centre for Advanced Materials and Biomaterials Research (CAMBR), The University of Western Ontario, 1151 Richmond St. N., London, Ontario, Canada, N6A 5B7. Telephone: ext (JBG). joe.gilroy@uwo.ca Table of Contents X-ray diffraction data collection and refinement details... S2 1 H and 13 C{ 1 H} and 31 P{ 1 H} NMR spectra... S3 UV-vis absorption spectra of 6a, 7a, 8a, and tris(ethylferrocene)phosphine oxide S10 Cyclic voltammograms of tris(ethylferrocene)phosphine oxide and 8a. S11 TDDFT calculations...s12 S1

2 Table S1. X-ray diffraction data collection and refinement details for complexes 7a, 7b, 8a, and 9a. 7a 7b 8a 9a Formula C 55 H 43 AlN 4 O 4 P 2 C 51 H 40 AlCl 2 N 5 O 4 P 2 C 43 H 67 AlN 4 O 4 P 2 C 91 H 91 AlFe 6 N 4 O 4 P 2 FW (g mol 1 ) Crystal Habit Purple Plate Purple Plate Purple Plate Purple Plate Crystal System Monoclinic Monoclinic Triclinic Triclinic Space Group C2/c P2 1 /c P1 P1 T (K) (Å) a (Å) (4) (5) (4) (2) b (Å) (7) (4) (4) (3) c (Å) (2) (2) (8) (4) (deg) (13) (6) (deg) (5) (9) (14) (6) (deg) (10) (4) V (Å 3 ) (19) (18) 4438(2) (13) Z (g cm 3 ) (cm 1 ) R 1, a R b 2 [I > 2σ] , , , , R 1, R 2 (all data) , , , , GOF c a R 1 = ( F o F c ) / F o, b R 2 = [ ( (F 2 o F 2 c ) 2 ) / ( F 4 o )] ½, c GOF = [ ( (F 2 o F 2 c ) 2 ) / (No. of reflns. No. of params.)] ½ S2

3 CHCl 3 CHCl H 2 O Figure S1. 1 H NMR spectrum of formazan 6a recorded in CDCl 3. The inset is an expansion of the aryl region. CDCl Figure S2. 13 C{ 1 H} NMR spectrum of formazan 6a recorded in CDCl 3. The inset is an expansion of the aryl region. S3

4 CHCl Figure S3. 1 H NMR spectrum of tris(ethylferrocene)phosphine oxide recorded in CDCl 3. CDCl Figure S4. 13 C{ 1 H} NMR spectrum of tris(ethylferrocene)phosphine oxide recorded in CDCl 3. The inset is an expansion of the signals associated with ferrocene. S4

5 CHCl Figure S5. 1 H NMR spectrum of complex 7a recorded in CDCl 3. The inset is an expansion of the aryl region. CDCl Figure S6. 13 C{ 1 H} NMR spectrum of complex 7a recorded in CDCl 3. The insets show expansions of the aryl region. S5

6 CHCl Figure S7. 1 H NMR spectrum of complex 7b recorded in CDCl 3. The inset is an expansion of the aryl region. CDCl Figure S8. 13 C{ 1 H} NMR spectrum of complex 7b recorded in CDCl 3. The inset is an expansion of the aryl region. S6

7 Figure S9. 1 H NMR spectrum of complex 8a recorded in CDCl 3. The inset is an expansion of the aryl region. a) b) c) CDCl Figure S C{ 1 H} NMR spectrum of complex 8a recorded in CDCl 3. The insets are expansions of the aryl (a) and alkyl (b) and (c) regions. S7

8 C 6 D 5 H C 6 D 5 H Figure S11. 1 H NMR spectrum of complex 9a recorded in C 6 D 6. The insets are expansions of the aryl region. C 6 D 6 C 6 D 6 a) b) Figure S C{ 1 H} NMR spectrum of complex 9a recorded in C 6 D 6. The insets are expansions of the aryl regions. S8

9 25 C 0 C 25 C 50 C 70 C 75 C 80 C 85 C 90 C Figure S13. Variable temperature 31 P{ 1 H} NMR spectra of complex 7a recorded in CD 2 Cl C 80 C Figure S14. Variable temperature 31 P{ 1 H} NMR spectra of complex 7a and one equivalent of triphenylphosphine oxide recorded in CD 2 Cl 2. S9

10 ε (M 1 cm 1 ) ε (M 1 cm 1 ) Normalized Intensity (a.u.) Normalized Intensity (a.u.) 1 (a) 1 (b) 0.8 7a + 50 OPPh 3 7a 0.8 8a + 50 OPBu a Wavelength (nm) Wavelength (nm) Figure S15. UV-vis absorption spectra of 5 µm CH 2 Cl 2 solutions of (a) complex 7a with 0 (black line) and 50 (red line) equivalents of triphenylphosphine oxide and (b) 8a with 0 (black line) and 50 (red line) equivalents of tri-n-butylphosphine oxide Wavelength (nm) Figure S16. UV-vis absorption spectrum of a 50 µm CH 2 Cl 2 solution of tris(ethylferrocene)phosphine oxide Wavelength (nm) Figure S17. UV-vis absorption spectrum of a 5 µm CH 2 Cl 2 solution of formazan 6a. S10

11 20 μa 20 µa 8a 8a + 50 OPBu Potential (V vs. Fc/Fc + ) Figure S18. Cyclic voltammograms of complex 8a containing 0 (black line) and 50 (blue line) equivalents of tri-n-butylphosphine oxide recorded in dry, degassed CH 2 Cl 2 containing ~1 mm analyte and 0.1 M [nbu 4 N][PF 6 ] at a scan rate of 0.25 V s μa 200 µa 9a Potential (V vs. Fc/Fc + ) Figure S19. Cyclic voltammogram of complex 9a recorded in dry, degassed CH 2 Cl 2 containing ~1 mm analyte and 0.1 M [nbu 4 N][PF 6 ] at a scan rate of 0.25 V s μa Potential (V vs. Fc/Fc + ) Figure S20. Cyclic voltammogram of tris(ethylferrocene)phosphine oxide recorded in dry, degassed CH 2 Cl 2 containing ~1 mm analyte and 0.1 M [nbu 4 N][PF 6 ] at a scan rate of 0.25 V s 1. S11

12 Table S2. Five lowest singlet-singlet electronic excitation energies of 7a in CH 2 Cl 2 solution calculated with TDDFT using various density functionals and the G(d,p) basis set. Non-equilibrium solvation effects are treated implicitly using the polarizable continuum model (PCM). The geometry of the complex is taken without re-optimization from X-ray measurements. Excitation λ max (ev) λ max (nm) Oscillator Strength, f M M06-2X PBE1PBE LC- PBE S12

13 # TD(NStates=5) M G(d,p) Int(Grid=UltraFine) SCRF=(PCM,Solvent=Dichloromethane) Al complex 7a 0,1 P Al O O N N C C C C H C H C H C H C C H C H C H C C H C H C H C H C H C C H C H C H C H S13

14 C H C C H C H C H C H C H O N N C C C H C H C H C H C H C H P O C C H C H C H C H C H C C H C H C H S14

15 C H C H C C H C H C H C H C H S15