Petru Poni Institute of Macromolecular Chemistry, Alea Gr. Ghica Voda 41A, , Iasi, Romania

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1 Supporting Information for Charge and Spin States in Schiff Base Metal Complexes with a Disiloxane Unit Exhibiting a Strong Non-innocent Ligand Character: Synthesis, Structure, Spectroelectrochemistry, and Theoretical Calculations Maria Cazacu, Sergiu Shova,*, Alina Soroceanu, Peter Machata, Lukas Bucinsky, Martin Breza, Peter Rapta,*, Joshua Telser, J. Krzystek, and Vladimir B. Arion*,# Petru Poni Institute of Macromolecular Chemistry, Alea Gr. Ghica Voda 41A, , Iasi, Romania Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, SK Bratislava, Slovak Republic Department of Biological, Chemical and Physical Sciences, Roosevelt University, 430 S Michigan Avenue, Chicago, Illinois, USA National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida, USA # Faculty of Chemistry, Institute of Inorganic Chemistry, University of Vienna, Währinger Strasse 42, A-1090 Vienna, Austria S1

2 (a) I / µa 6 0 (b) I / µa E vs. DmFc + /DmFc / V -8 (c) E vs. DmFc + /DmFc / V 2 I / µa mv s mv s mv s -1 5 mv s E vs. DmFc + /DmFc / V Figure S1. Cyclic voltammograms of copper complexes 4 (black line), 5 (red line), and 6 (blue line) in the (a) anodic and (b) cathodic regions, measured in TBAPF 6 /CH 2 Cl 2 at Pt working electrode (scan rate 100 mv s 1 ). (c) Cyclic voltammograms of 5 in the cathodic region in TBAPF 6 /CH 2 Cl 2 measured at different scan rates (indicated on figure). S2

3 16 8 CH 2 Cl 2 + TBAPF I / µa E vs. DmFc + /DmFc / V Figure S2. Cyclic voltammograms of TBAPF 6 /CH 2 Cl 2 (black dashed line) and 0.5 mm complexes 1 (green line), 2 (red line), and 3 (blue line) both in the anodic and cathodic regions, measured in TBAPF 6 /CH 2 Cl 2 at Pt working electrode (scan rate 100 mv s 1 ). S3

4 ε / l mol -1 cm λ / nm Figure S3. Optical spectra of 0.5 mm complexes 1 3 in dichloromethane. S4

5 1 [1] 0 : ev / 397 nm, α,β-homo α,β-lumo 1 [1] 0 : ev / 347 nm, α,β-homo 1 α,β-lumo+1 Figure S4. Molecular orbitals calculated using B3LYP functional that contribute dominantly to the lowest TD-B3LYP electronic transitions (energies listed) for 1 [1] 0 (isosurface at atomic units). The values in italics are oscillator strengths. S5

6 2 [2] 0 : ev / 339 nm, β HOMO 4 β-lumo α-homo α-lumo+1 2 [2] 0 : ev / 442 nm, β-homo β-lumo S6

7 β-homo-9 β-lumo Figure S5. Molecular orbitals calculated using B3LYP functional that contribute dominantly to the lowest TD-B3LYP electronic transitions (energies listed) for 2 [2] 0. The values in italics are oscillator strengths. S7

8 5 [3] 0 : ev / 677 nm, α-homo α-lumo 5 [3] 0 : ev / 808 nm, α-homo 2 α-lumo Figure S6. Molecular orbitals calculated using B3LYP functional that contribute dominantly to the lowest TD-B3LYP electronic transitions (energies listed) for 5 [3] 0. The values in italics are oscillator strengths. S8

9 Figure S7. HFEPR spectrum of 3 at 10 K and 208 GHz (black trace), accompanied by two simulations. Red trace: simulation using only 2 nd -rank zfs parameters as in main text; blue trace: simulation adding a 4 th -rank zfs parameter, 4 B 4 = cm 1. S9

10 Table S1. Crystallographic data, details of data collection and structure refinement parameters for NiL 0.5CH 2 Cl 2 (1 0.5CH 2 Cl 2 ), CuL 1.5H 2 O (2 1.5H 2 O) and MnL(OAc) 0.15H 2 O (3 0.15H 2 O). NiL 0.5CH 2 Cl 2 CuL 1.5H 2 O MnL(OAc) 0.15H 2 O empirical formula C 40.5 H 67 NiClN 2 O 3 Si 2 C 40 H 66 CuN 2 O 3 Si 2 C 42 H 69.3 MnN 2 O 5.15 Si 2 M r T [K] λ [Å] crystal system monoclinic Monoclinic triclinic space group P2 1 /n P2 1 /n P a [Å] (6) (12) (13) b [Å] (19) (3) (2) c [Å] (3) (2) (18) α [ ] (8) β [ ] (8) (12) (7) γ [ ] (7) V [Å 3 ] 4685(3) (10) (10) Z ρ (calcd.) [g cm 3 ] crystal size [mm] Reflections collected/unique 23354/9192 [R int = ] 20612/8779 [R int = ] 75413/24946 [R int = ] µ, [mm 1 ] R a 1 (I>2σ(I)) R b 2 (all data) GOF c ρ max and ρ min 0.79 and and and 0.56 [eå 3 ] a R 1 = Σ F o - F c /Σ F o, b wr 2 = {Σ[w (F 2 o - F 2 c ) 2 ] /Σ[w(F 2 o ) 2 ]} 1/2. c GOF = {Σ[w(F 2 o - F 2 c ) 2 ] /(n p)} 1/2, where n is the number of reflections and p is the total number of parameters refined. S10

11 Table S2. Selected experimental bond lengths (Å) and angles ( ) for NiL 0.5CH 2 Cl 2 (1 0.5CH 2 Cl 2 ), CuL 1.5H 2 O (2 1.5H 2 O) and MnL(OAc) 0.15H 2 O (3 0.15H 2 O). NiL 0.5CH 2 Cl 2 CuL 1.5H 2 O MnL(OAc) 0.15H 2 O A B C Si1 O3 Si2 O3 N1 M1 N2 O2 M1 N1 O2 M1 N2 O2 M1 O1 O1 M1 N1 O1 M1 N2 O1 M1 O4 O1 M1 O5 N2 M1 O4 N2 M1 O5 O4 M1 O5 N1 M1 O4 N1 M1 O5 O2 M1 O4 O2 M1 O5 Si1 O3 Si2 a) τ 4 a) 1.619(4) 1.610(4) 1.571(5) 1.584(5) 1.588(5) 1.621(4) 1.616(3) 1.609(6) 1.594(5) 1.573(5) 169.9(1) 153.1(2) 119.8(2) 120.0(2) 119.3(2) 91.9(1) 92.5(1) 88.6(2) 89.7(2) 90.6(2) 88.6(1) 92.5(1) 87.0(2) 85.8(2) 87.8(2) 170.1(1) 154.2(1) 175.5(2) 175.5(2) 176.4(2) 89.0(1) 92.7(1) 88.4(2) 87.6(2) 87.4(2) 92.3(1) 94.3(1) 91.6(2) 92.5(2) 90.7(2) (2) 90.5(2) 92.3(2) (2) 91.0(2) 90.4(2) (2) 145.2(2) 94.5(2) (2) 87.2(2) 154.1(2) (2) 58.1(2) 59.6(2) (2) 94.8(2) 146.2(2) (2) 152.9(2) 86.6(2) (2) 93.3(2) 91.1(2) (2) 93.0(2) 92.5(2) 160.6(3) 161.1(3) 154.7(5) 166.3(4) 177.8(4) ( α+ β ) τ 4 =, where α and β are the two largest θ angles at M1 atom. 141 S11

12 Table S3. DFT energies (E DFT ) and free energies at 298 K (G 298 ) obtained by unrestricted formalism (UB3LYP) of the UB3LYP optimized structures under study and corresponding values obtained by restricted formalism (ROB3LYP) for the same geometries System UB3LYP ROB3LYP E DFT [hartree] G 298 [hartree] E DFT [hartree] 1 [1] a) a) [1] [1] [1] [1] a) [1] [1] [2] [2] a) a) [2] [2] [2] [3] a) a) [3] [3] [3] [3] a) broken symmetry treatment S12

13 Table S4. Selected bond lengths (Å) and bond angles ( o ) of [1] 0, [2] 0 and [3] 0 obtained by DFT geometry optimization. Compound 1 [1] 0 3 [1] 0 2 [2] 0 1 [3] 0 3 [3] 0 5 [3] 0 Si1-O Si2-O Bond angles N1 M1 N O2 M1 N O2 M1 N O2 M1 O O1 M1 N O1 M1 N O1 M1 O O1 M1 O N2 M1 O N2 M1 O O4 M1 O N1 M1 O N1 M1 O O2 M1 O O2 M1 O Si1 O3 Si a) τ a) 360 ( α+ β ) τ 4 =, where α and β are the two largest θ angles at M1 atom. 141 S13

14 Table S5. Calculated EPR parameters (g, D, E and A) at B3LYP and BLYP levels of theory using the 6-311G* (denoted B1) and a mix of basis sets (denoted B2) for different atoms (6-311+G* for N,O and the central metal atom; 6-311G* for C and H atoms). If not otherwise stated DFT optimized geometries are employed. Details g xx g yy g zz g iso D [cm -1 ] E/D A xx [MHz] A yy [MHz] A zz [MHz] A iso [MHz] 2 [1] 1 B1 a) B1 a)b) B1 c) B2 a) B2 a)b) B2 c) [1] 0 B1 a) B1 a)b) B1 c) B2 a) B2 a)b) B2 c) [2] 1 B1 a) B1 a)b) B1 c) B2 a) B2 c) [2] 0 B1 a) B1 a)b) B1 c) B2 a) B2 c) [3] + B1 a) B1 a)b) B1 c) B2 a) B2 c) [3] 0 B1 a) B1 a)d) ,01-119,69-202,78-144,16 B1 a)b) B1 c) B1 c)d) B2 a) B2 c) a) B3LYP, b) COSMO solvation model of CH 2 Cl 2, c) BLYP, d) Experimental X-ray geometry C S14