Symmetry breaking charge transfer as a means to study electron transfer with no driving force

Kellogg, Michael; Akil, Ali; Muthiah Ravinson, Daniel Sylvinson; Estergreen, Laura; Bradforth, Stephen E.; Thompson, Mark E.

doi:10.1039/c8fd00201k

Symmetry breaking charge transfer as a means to study electron transfer with no driving force

Journal Article · Sun Jan 13 23:00:00 EST 2019 · Faraday Discussions

DOI:https://doi.org/10.1039/c8fd00201k· OSTI ID:1735839

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Univ. of Southern California, Los Angeles, CA (United States); University of Southern California
Univ. of Southern California, Los Angeles, CA (United States)

Symmetry breaking charge transfer (SBCT) is a process where a symmetrically disposed pair of identical chromophores forms a charge transfer excited state with the hole and electron on different chromophores, i.e. chr–chr + hν → chr⁺–chr^–. Herein we explore this process in two dipyrrin-based bichromophoric systems. One of these bisdipyrrins involved a pair of BODIPY chromophores linked by a single bond at their meso-positions (compound 1) and the other involved two dipyrrin ligands coordinated in a tetrahedral geometry at the Zn²⁺ ion (compound 2). Both compounds show rapid SBCT in polar solvents and only dipyrrin based emission in nonpolar solvents, the latter arising from a dipyrrin localized excited sate (LE). By “tuning” the solvent polarity the equilibrium between the LE and SBCT states can be shifted to favor either state. Ultrafast transient absorption spectroscopy (TA) was used to probe the kinetics of the charge transfer for 2 in solvents where the electron transfer is endergonic, exergonic and has a ΔG close to zero. Our TA derived rates were used to predict fluorescence efficiencies in each of the different solvent systems and showed a good correspondence to measured values. Detailed density functional theory (DFT) and time dependent DFT were used to model the ground states as well as the LE and SBCT states of 1 and 2, in both polar and nonpolar media. Lastly, the ground and LE excited states show small dipole moments, while the SBCT states show dipole moments of 16.4 and 20.3 D for 1 and 2, respectively.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0016450

OSTI ID:: 1735839

Alternate ID(s):: OSTI ID: 1508861
OSTI ID: 1612573

Journal Information:: Faraday Discussions, Journal Name: Faraday Discussions Vol. 216; ISSN 1359-6640

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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