Methylene Blue Exciton States Steer Nonradiative Relaxation: Ultrafast Spectroscopy of Methylene Blue Dimer.

The photochemistry and aggregation properties of methylene blue (MB) lead to its popular use in photodynamic therapy. The facile formation of strongly coupled "face-to-face" H-aggregates in concentrated aqueous solution, however, significantly changes its spectroscopic properties and photophysics. The photoinitiated dynamics of the simplest MB aggregate, MB2, was investigated over femtosecond to nanosecond time scales revealing sequential internal conversion events that fully relax the excited population. MB monomer dynamics were analyzed in tandem for a direct comparison. First, ultrafast internal conversion from the electric-dipole allowed upper exciton state to the lower forbidden exciton state was evaluated by use of broadband transient absorption (BBTA) and two-dimensional electronic spectroscopy (2DES) with a time resolution of ∼ 10 fs. Lineshape analysis of MB and MB2 2DES bands at 298 and 77 K show effectively no difference in the diagonal/antidiagonal line width ratio for the dimer, in marked contrast to the distinct reduction of the homogeneous line width for MB. This result is interpreted as ultrafast population relaxation imposing a limitation to the homogeneous line width, instead of pure dephasing as in the case of the monomer. Narrowband transient absorption was performed with the aid of target analysis, to model the dynamics at longer times. The MB dynamics were described by a sequential model featuring vibrational relaxation (1-10 ps) followed by intersystem crossing and internal conversion (τ ∼ 370 ps) leaving behind MB triplet species. Alternatively, the dimer dynamics were entirely quenched within ∼ 10 ps, yielding a ground state recovery time of 3-4 ps. Such fast and complete relaxation to the ground state demonstrates the effect of concentration quenching when monomers are brought into close proximity. The formation of exciton states introduces an initial energy funnel that eventually leads to population relaxation to the ground state, preventing even the dissociation of dimers despite having internal energies well above its binding energy.