Supporting Information

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1 Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the Owner Societies 2017 Supporting Information for Photodissociation of EtPhCbl Antivitamin B 12 Piotr Lodowski, 1 Karolina Ciura, 1 Megan J. Toda, 2 Maria Jaworska, 1 and Pawel M. Kozlowski* 2,3 1 Department of Theoretical Chemistry, Institute of Chemistry, University of Silesia in Katowice, Szkolna 9, PL Katowice, Poland 2 Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, United States 3 Visiting professor, Department of Food Sciences, Medical University of Gdansk, Al. Gen. J. Hallera 107, Gdansk, Poland *Phone: (502) Fax: (502) pawel@louisville.edu

2 Table S1. TD-DFT excitation energies, oscillator strengths, parameters, composition and characters of ten low-lying, singlet electronic transitions for the Im-[Co III (corrin)]-etph + model complex based on the BP86/TZVPP calculations with use PCM solvent model. E(eV) λ(nm) f % character S H-1 L π + d xz π * H-2 L d xz + π Ph π * S H L d yz + π π * H-1 L π + d xz π * S H-2 L d xz + π Ph π * H-1 L π + d xz π * H L d yz + π π * S H-3 L d x2-2 y π * S H L+1 d yz + π d xy - n H-4 L π Ph + d xz π * H-2 L+1 d xz + π Ph d xy - n H L+2 d yz + π d xy - n + π * S H-1 L+1 π + d xz d xy - n H-1 L+2 π + d xz d xy - n + π * S H-4 L π Ph + d xz π * H-2 L+1 d xz + π Ph d xy - n H L+2 d yz + π d xy - n + π * S H L+2 d yz + π d xy - n + π * H L+3 d yz + π σ * (d z2 ) - n S H-5 L π Ph + π Im π * H L+3 d yz + π σ * (d z2 ) - n S H-6 L π Ph + π Im π * 2

3 Table S2. TD-DFT excitation energies, oscillator strengths, parameters, composition and characters of ten low-lying, singlet electronic transitions for the [Co III (corrin)]-etph + model complex (base-off form of Im-[Co III (corrin)]-etph + ) based on the BP86/TZVPP calculations with use PCM solvent model. E(eV) λ(nm) f % character S H-1 L π Ph + d xz π * H L+1 d yz + π σ * (d z2 ) n S H-1 L π Ph + d xz π * H L+1 d yz + π σ * (d z2 ) - n H L d yz + π π * S H-1 L+1 π Ph + d xz σ * (d z2 ) n S H L d yz + π π * H L+1 d yz + π σ * (d z2 ) n S H-2 L d x2-2 y π * S H-2 L+1 d x2-2 y σ * (d z2 ) n H-3 L+1 π+d yz σ * (d z2 ) n H-1 L+3 π Ph + d xz π * + d xz S H L+2 d yz + π d xy n H L+3 d yz + π π * + d xz H-3 L π+d yz π * H-1 L+2 π Ph + d xz d xy n S H-3 L π+d yz π * H-4 L π Ph + d xz π * H-2 L+1 d x2-2 y σ * (d z2 ) n H L+3 d yz + π π * + d xz S H L+3 d yz + π π * + d xz H-3 L+1 π+d yz σ * (d z2 ) n H L+2 d yz + π d xy n H-2 L+1 d x2-2 y σ * (d z2 ) n S H-5 L π Ph π * H-4 L π Ph + d xz π * H L+2 d yz + π d xy n 3

4 Table S3. TD-DFT excitation energies, oscillator strengths, parameters, composition and characters of transitions for optimized geometry of the S 1 singlet excited state of Im-[Co III (corrin)]- EtPh + model complex at selected points on the S 1 PES. Location of selected points on the S 1 surface shown below table. Results based on the BP86/TZVPP calculations with use PCM solvent model. R Co-C (Å) R Co-N (Å) E(eV) λ(nm) f % character I S H L d xz + π + π Ph π * IVB S 1(min1) H L (d xz +d yz ) + π Ph π * IIIB S 1(min2) H L (d xz +d yz ) + π Ph * (d z2 ) - n + π * P H L d xz + π + π Ph π * P H L (d xz +d yz ) + π + π Ph π * 15 H-1 L (d xz -d yz ) + π π * P H L (d xz +d yz ) - n + π Ph π * 11 H-1 L (d xz -d yz ) + π + π Ph π * P H L (d xz +d yz ) - n + π Ph π * P H L (d xz +d yz ) - n + π Ph π * 35 H-1 L (d xz -d yz ) + π + π Ph π * P H L (d xz +d yz ) - n + π Ph * (d z2 )-n + π * P H L (d xz +d yz ) - n + π Ph * (d z2 )-n 4

5 Figure S1. (a) Molecular structure of antivitamin B 12, 4-ethylphenylcobalamin (EtPhCbl) and (b) structure of model complex used in calculations. The full structure of EtPhCbl is drawn based on the crystallographic structure from M. Ruetz, C. Gherasim, K. Gruber, S. Fedosov, R. Banerjee, B. Kräutler, Access to Organometallic Arylcobaltcorrins through Radical Synthesis: 4-Ethylphenylcobalamin, a Potential Antivitamin B 12, Angew. Chem. Int. Ed. 2013, 52, , and CCDC data obtained from the Cambridge Crystallographic Data Centre via 5

6 Figure S2. Potential energy surfaces (PESs) for ground state and two lowest excited states of Im-[Co III (corrin)]-etph + model complex together with vertical projections of PES for S 0, S 1 and S 2 electronic states, plotted as a function of axial bond lengths calculated in water solution (COSMO) at BP86/TZVPP level of theory. The vertical projections plots have separate color scales. 6

7 Figure S3. Energy diagram of molecular orbitals involved in electronic excitations to S 1 and S 2 excited states for optimized S 1 geometries of Im-[Co III (corrin)]-etph + model complex at minimum energy and two points of S 1 PES located near the S 1 /S 2 intersection. P 5 and P 6 refer to selected points on S 1 PES shown in Table S3. 7

8 Figure S4. Selected molecular orbitals involved in vertical electronic excitations for the Im-[Co III corr]-etph + model complex in the ground state S 0, obtained from DFT/BP86 level of theory. 8

9 Figure S5. Selected molecular orbitals involved in vertical electronic excitations for the [Co III (corrin)]-etph + model complex (base-off form of Im-[Co III (corrin)]-etph + ) in the ground state S 0, obtained from DFT/BP86 level of theory. 9