Abstract
We have studied two regioisomeric terrylenediimide (TDI) dimers in which the 1-positions of two TDIs are linked via 1,3- or 1,4-phenylene spacers, mTDI2 and pTDI, respectively. The nature and the dynamics of the multiexciton state are tuned by altering the through-bond electronic couplings in the ground and excited states and by changing the solvent environment. Our results show that controlling the electronic coupling between the two chromophores by an appropriate choice of linker can result in independent triplet state formation, even though the initial correlated triplet pair state is confined to a dimer. Moreover, even in polar solvents, if the electronic coupling is strong, the correlated triplet pair state is observed prior to symmetry-breaking charge separation. These results point out the close relationship between the singlet, correlated triplet pair, and charge transfer states in molecular dimers.
| Original language | English (US) |
|---|---|
| Article number | 244306 |
| Journal | Journal of Chemical Physics |
| Volume | 153 |
| Issue number | 24 |
| DOIs | |
| State | Published - Dec 28 2020 |
Funding
We thank Jonathan D. Shultz for assisting in the computational work. This work was supported by the Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award No. DE-FG02-99ER14999. Y.J.B. and M.C. gratefully acknowledge support from the Ryan Fellowship and the International Institute for Nanotechnology at Northwestern University. This work was supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1842165 (S.M.H.). This work made use of the IMSERC at Northwestern University, which received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (Grant No. NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357.
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry