TY - JOUR
T1 - Charge-transfer biexciton annihilation in a donor-acceptor co-crystal yields high-energy long-lived charge carriers
AU - Schlesinger, Itai
AU - Powers-Riggs, Natalia E.
AU - Logsdon, Jenna L.
AU - Qi, Yue
AU - Miller, Stephen A.
AU - Tempelaar, Roel
AU - Young, Ryan M.
AU - Wasielewski, Michael R.
N1 - Funding Information:
This work was supported by the US National Science Foundation under Award DMR-2003739 (M. R. W.). I. S. would like to thank Yad Hanadiv Foundation for the Rothschild Postdoctoral Fellowship. N. E. P-R. was supported by NSF Graduate Research Fellowship (DGE-1324585). Crystal diffraction data made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). We thank Dr C. Stern for additional guidance in crystal structure solution refinement.
Funding Information:
This work was supported by the US National Science Foundation under Award DMR-2003739 (M. R. W.). I. S. would like to thank Yad Hanadiv Foundation for the Rothschild Postdoctoral Fellowship. N. E. P-R. was supported by NSF Graduate Research Fellowship (DGE-1324585). Crystal diffraction data made use of the IMSERC at Northwestern University, which has received support from the So and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). We thank Dr C. Stern for additional guidance in crystal structure solution renement.
Publisher Copyright:
© The Royal Society of Chemistry 2020.
PY - 2020/9/21
Y1 - 2020/9/21
N2 - Organic donor-acceptor (D-A) co-crystals have attracted much interest due to their important optical and electronic properties. Co-crystals having ⋯DADA⋯ π-stacked morphologies are especially interesting because photoexcitation produces a charge-transfer (CT) exciton, D˙+-A˙−, between adjacent D-A molecules. Although several studies have reported on the steady-state optical properties of this type of CT exciton, very few have measured the dynamics of its formation and decay in a single D-A co-crystal. We have co-crystallized aperi-xanthenoxanthene (PXX) donor with aN,N-bis(3-pentyl)-2,5,8,11-tetraphenylperylene-3,4:9,10-bis(dicarboximide) (Ph4PDI) acceptor to give an orthorhombicPXX-Ph4PDI⋯DADA⋯ π-stacked co-crystal with a CT transition dipole moment that is perpendicular to the transition moments for Sn← S0excitation ofPXXandPh4PDI. Using polarized, broadband, femtosecond pump-probe microscopy, we have determined that selective photoexcitation ofPh4PDIin the single co-crystal results in CT exciton formation within the 300 fs instrument response time. At early times (0.3 ≤t≤ 500 ps), the CT excitons decay with at−1/2dependence, which is attributed to CT biexciton annihilation within the one-dimensional ⋯DADA⋯ π-stacks producing high-energy, long-lived (>8 ns) electron-hole pairs in the crystal. These energetic charge carriers may prove useful in applications ranging from photovoltaics and opto-electronics to photocatalysis.
AB - Organic donor-acceptor (D-A) co-crystals have attracted much interest due to their important optical and electronic properties. Co-crystals having ⋯DADA⋯ π-stacked morphologies are especially interesting because photoexcitation produces a charge-transfer (CT) exciton, D˙+-A˙−, between adjacent D-A molecules. Although several studies have reported on the steady-state optical properties of this type of CT exciton, very few have measured the dynamics of its formation and decay in a single D-A co-crystal. We have co-crystallized aperi-xanthenoxanthene (PXX) donor with aN,N-bis(3-pentyl)-2,5,8,11-tetraphenylperylene-3,4:9,10-bis(dicarboximide) (Ph4PDI) acceptor to give an orthorhombicPXX-Ph4PDI⋯DADA⋯ π-stacked co-crystal with a CT transition dipole moment that is perpendicular to the transition moments for Sn← S0excitation ofPXXandPh4PDI. Using polarized, broadband, femtosecond pump-probe microscopy, we have determined that selective photoexcitation ofPh4PDIin the single co-crystal results in CT exciton formation within the 300 fs instrument response time. At early times (0.3 ≤t≤ 500 ps), the CT excitons decay with at−1/2dependence, which is attributed to CT biexciton annihilation within the one-dimensional ⋯DADA⋯ π-stacks producing high-energy, long-lived (>8 ns) electron-hole pairs in the crystal. These energetic charge carriers may prove useful in applications ranging from photovoltaics and opto-electronics to photocatalysis.
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U2 - 10.1039/d0sc03301d
DO - 10.1039/d0sc03301d
M3 - Article
C2 - 34094218
AN - SCOPUS:85092211528
VL - 11
SP - 9532
EP - 9541
JO - Chemical Science
JF - Chemical Science
SN - 2041-6520
IS - 35
ER -