The photophysics of naphthalene dimers controlled by sulfur bridge oxidation

Oxidation state of bridge controls the deactivation mechanism of naphthalene dimers.

. Vertical transition energies to the lowest excited bright singlet state for the anti-D2 dimer computed with different functionals and conditions. Table S2. Vertical transition energies to the lowest excited bright singlet state for the anti-D2 dimer computed at the TDDFT ωB97X-D level with different basis Table S3. Vertical transition energies ΔE (in eV) and oscillator strengths (f) for the naphthalene-SO n -Me molecules in DCM computed at the ωB97X-D/6-31+G(d) level. Table S4. Vertical transition energies ΔE (in eV), oscillator strength (f), electronic character (in %) LE (on naphthalene fragments), CT (between naphthalene moieties) and CT B (from the SO n bridge to the naphthalenes) and electronic couplings between the lowest LE, CT and CT B diabatic states (in meV) for the lowest excited singlet of the different conformers of D0, D1 and D2 dimers in DCM computed at the ωB97X-D/6-31+G(d) level. Table S5. Estimated relative PL quantum yields (without considering non-radiative decay pathways) obtained as the numerical integration of the emission profiles of Dn dimers in DCM considering (i) ground state population (S 0 ) and (ii) excited state population (S 1 ) compared to the experimental yields from J. Amer. Chem. Soc, 135 (2013) 8109. Table S6. S1/S0 energy gaps (in kcal/mol) at the inversion TS of D1 (syn and anti) and D2 (anti) dimers estimated as: ΔE(S 1 /S 0 ) = ΔE(S 0 S 1 ) -λ(S 1 ) + ΔE(TS,S 1 ) -ΔE(TS,S 0 ), where ΔE(S 0 S 1 ) is the vertical gap at the Franck-Condon geometry, λ(S 1 ) is the reorganization energy of S 1 , and ΔE(TS,S 0 ) and ΔE(TS,S 1 ) are the energy barriers at the S 0 transition state geometry on the S 0 and S 1 PES, respectively. Electronic Supplementary Material (ESI) for Chemical Science. This journal is © The Royal Society of Chemistry 2017 Figure S1. Most stable conformers for the ground state of Dn dimers in DCM solution. Figure S2. Ground and first excited state energy profiles for the interconversion between conformers of the D0 dimer in DCM solution computed at the ωB97X-D/6-31+G(d) level. All structures have been relaxed on the ground state PES.          Table S6. S1/S0 energy gaps (in kcal/mol) at the inversion TS of D1 (syn and anti) and D2 (anti) dimers estimated as:

TABLES
is the vertical gap at the Franck-Condon geometry, λ(S 1 ) is the reorganization energy of S 1 , and ΔE(TS,S 0 ) and ΔE(TS,S 1 ) are the energy barriers at the S 0 transition state geometry on the S 0 and S 1 PES, respectively.  sym-CI asym-CI

Transition states for the structural inversion
The transition states for the structural inversion of D1 and D2 were characterized as first order saddle points while those of D0 were second order saddle points on the ground state PES. This second order saddle point which corresponds to a linear structure of D0 is a transition state connecting two transition states (first order saddle points). These latter transition states connect the two enantiomers of syn and anti ground state conformers respectively.

CI relative energies
The values of ΔE(rel) for inv-TS and sym-CI ( Note. The derivative coupling vectors correspond to the same nuclear motion as the imaginary frequencies of the transition states of D1 and D0. Therefore, the nuclear motion that lowers the energy from the transition states to the ground state minima is equivalent to the motion that opens the gap of the S 0 /S 1 crossing.

Transition state structures for the inversion of Dn dimers (in Angstroms).
Saddle point for the inversion of syn-D0