Influence of methoxy groups on the properties of 1,1-bis(4-aminophenyl) cyclohexane based arylamines: experimental and theoretical approach

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1 Influence of methoxy groups on the properties of 1,1-bis(4-aminophenyl) cyclohexane based arylamines: experimental and theoretical approach Jonas Keruckas 1, Ramunas Lygaitis, Jurate imokaitiene, Juozas Vidas Grazulevicius*, Vygintas Jankauskas and Gjergji ini 3 * upporting information Table 1. a Values of Δd parameter (Å) (defined here as sum of differences between every two consecutive bond lengths inside a Ph ring) calculated for the internal (un-substituted) and external (substituted) Ph rings. b ΔE(H-H -1 ) corresponds to the energy splitting between the and -1 orbitals for each neutral compound neutral cation neutral cation neutral cation neutral cation Ph-internal a Ph-external a E(H-H -1 ) (ev) b Table. Transition energies and oscillator strengths obtained from the TDDFT calculations at the B3LYP/6-31+G* level Excited state Energy (ev) f a Energy (ev) f a Energy (ev) f a Energy (ev) f a The excitation energies are in ev. a Oscillator strengths. 1 Department of Organic Technology, Kaunas University of Technology, Radvilenu plentas 19, LT-04, Kaunas, Lithuania Department of olid tate Electronics, Vilnius University, auletekio aleja 9, LT-, Vilnius, Lithuania 3 Laboratoire de Physicochimie des Polymères et des Interfaces, EA 8 Université de Cergy-Pontoise, mail Gay-Lussac, 9031 Cergy-Pontoise Cedex * Corresponding authors s: juozas.grazulevicius@ktu.lt, gjergji.sini@u-cergy.fr

2 1.398 (1.397) (1.39) 41.8 (4.4) (.449) (1.384) 41.3 (3.) (1.43) 1.41 (1.4) (1.403) (1.4) (1.389) 40.6 (44.) a Compound 1 b Compound (1.389) (1.408) (1.3).493 (.41) (1.396) 41. (4.8) (1.397) 1.401(1.40) 1.41 (1.43) 1.41 (1.4) (1.384) (1.40) (33.) (1.411) (1.389) (1.409) 1407 (1.407) 41.8 (44.1) c Compound 3 Compound 4 Figure 1. Optimized geometries for the compounds 1-4 along withsome typical bond-lengths (Å) and dihedral anglesbetween the Ph rings and the Nplane (absolute values in degrees, indicated inside the Ph rings). The values in parenthesis correspond to the radical cation state. Atoms in red, grey, blue, and white colors are oxygen, carbon, nitrogen, and hydrogen respectively.

3 a b c d Figure. UV-VI absorption spectra obtained from TDDFT calculations at the B3LYP/6-31+G* level: a, b c and d correspond to the compounds 1-4 respectively. The absorption bands are obtained by considering peak half-widths at half heightof 0.333eV.It can be observed that the λ UVmax for 1 and 4 are not due to the strongest transition but to the sum of some higher energy transitions which are very close in energy.

4 -1 LUMO+ LUMO+3 LUMO+4 LUMO+ Figure 3. Pictograms of some relevant molecular orbitals for the compound 4.

5 ome details on the estimation of k HT values The k HT values are calculated on the basis of the Marcus-Levich-Jortner equation: k CT 4 h 1 t 4 k T s B n 0 n ( G s n i ) exp( ) exp n! 4k BsT (eq. 1) In this equation: tis the electronic coupling between two adjacent molecules, G is the CT reaction free energy (set to zero in the case of hole transfer between identical molecules),sis themedium (outer) reorganization energy (set to 0.3 ev for all the compounds 1- i 4), i is the Huang-Rhys factor characterizing the strength of the electron-vibration coupling for the internal mode i (in the products).i, i represents the energetic effort due to the intra-molecular geometric relaxations related to the CT between two adjacent molecules. In this calculation, the vibration mode hω i has been set equal to 0.eV, which is a typical value for the energy of a carbon-carbon bond stretch in a conjugated system (V. Lemaur, M. teel, D. Beljonne, J.L. Bredas, J. Cornil, J. Am. Chem. oc. 00, 17, ). The transfer integrals between frontier orbitals of two monomers in a dimerwere calculated on the basis of the following equation (E.F. Valeev, V. Coropceanu, D.A. da ilva,. alman, J.L. Bredas, J. Am. Chem. oc. 006, 18, 988): t 1 ~ 1 t1 ( ~ ~ 1 ) (Eq. ) The parameters involved in this formula are calculated as follows (for example in the case of the transfer integral between the 1 orbitals of two monomers, noted here as M1 and M): ~ M1 1 ˆ M t H dim er (Eq. 3) ~ M1( M ) 1( ) 1() ˆ M M H dimer (Eq. 4) 1 M 1 M (Eq. ) 0 In the above equations, ˆ monomers, whereas H dim er M 1( M ) represent the wave functions corresponding to M1 and M as calculated from the isolated is the Hamiltonian in a given geometry of the dimer M1 M. The necessary matrices for these calculations ( 1 and 1 ~ t ) are produced by Gaussian09 program.