Temperature-Dependent Mechanistic Transition for Photoinduced Electron Transfer Modulated by Excited-State Vibrational Relaxation Dynamics

Abstract

The electron transfer (ET) dynamics of an unusually rigid pi-stacked (porphinato)zinc(II)-spacer-quinone (PZn-Q) system, [5-[8'-(4' '-[8' ''-(2' '' ',5' '' '-benzoquinonyl)-1' ''-naphthyl]-1' '-phenyl)-1'-naphthyl]-10,20-diphenylporphinato]zinc(II) (2a-Zn), in which sub-van der Waals interplanar distances separate juxtaposed porphyryl, aromatic bridge, and quinonyl components of this assembly, have been measured by ultrafast pump-probe transient absorption spectroscopy over a 80-320 K temperature range in 2-methyl tetrahydrofuran (2-MTHF) solvent. Analyses of the photoinduced charge-separation (CS) rate data are presented within the context of several different theoretical frameworks. Experiments show that at higher temperatures the initially prepared 2a-Zn vibronically excited S1 state relaxes on an ultrafast time scale, and ET is observed exclusively from the equilibrated lowest-energy S1 state (CS1). As the temperature decreases, production of the photoinduced charge-separated state directly from the vibrationally unrelaxed S1 state (CS2) becomes competitive with the vibrational relaxation time scale. At the lowest experimentally interrogated temperature ( approximately 80 K), CS2 defines the dominant ET pathway. ET from the vibrationally unrelaxed S1 state is temperature-independent and manifests a subpicosecond time constant; in contrast, the CS1 rate constant is temperature-dependent, exhibiting time constants ranging from 4x10(10) s(-1) to 4x10(11) s(-1) and is correlated strongly with the temperature-dependent solvent dielectric relaxation time scale over a significant temperature domain. Respective electronic coupling matrix elements for each of these photoinduced CS1 and CS2 pathways were determined to be approximately 50 and approximately 100 cm-1. This work not only documents a rare, if not unique, example of a system where temperature-dependent photoinduced charge-separation (CS) dynamics from vibrationally relaxed and unrelaxed S1 states can be differentiated, but also demonstrates a temperature-dependent mechanistic transition of photoinduced CS from the nonadiabatic to the solvent-controlled adiabatic regime, followed by a second temperature-dependent mechanistic evolution where CS becomes decoupled from solvent dynamics and is determined by the extent to which the vibrationally unrelaxed S1 state is populated.

Electron transfer reactions of rigid, cofacially compressed, π-stacked porphyrin–bridge–quinone systems

“…The slower rising component (k 1 , 1 ) exhibited an unusual temperature dependence while the faster one (k 2 , 2 ) was nearly temperature independent over all temperature ranges. It is important to note that the ratio of amplitudes of these two components (A 1 /A 2 , 1 > 2 ) became smaller as the temperature decreased [152]. The sole decay component ( 3 ) is assigned as CR in these cases.…”

“…For the QM calculation, an inner-sphere reorganization energy i = 0.5 eV and an averaged single high-frequency vibrational quantumh ω = 1600 cm −1 were used. The temperature dependent inverse longitudinal relaxation times of 2-MTHF ( −1 L ) are shown as black triangles [152]. [204,[270][271][272][273][274][275][276][277][278][279][280][281][282].…”

“…(26). The temperature dependent solvent longitudinal relaxation rate constants ( −1 L ) for 2-MTHF are depicted as black triangles [152]. 100 cm −1 .…”

“…The best biexponential function fit for 310 K and the triexponential function fits for 120 K and 80 K are depicted by thin lines. Experimental conditions: ex = 557 nm, solvent = 2-MTHF, magic angle polarization[152].…”

“…Deduced electronic coupling matrix elements and activation barriers for the two apparent linear regimes are shown as insets[152].…”