TY - JOUR
T1 - Spin-Selective Photoinduced Electron Transfer within Naphthalenediimide Diradicals
AU - La Porte, Nathan T.
AU - Christensen, Joseph A.
AU - Krzyaniak, Matthew D.
AU - Rugg, Brandon K.
AU - Wasielewski, Michael R.
N1 - Funding Information:
This research was supported by the Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0019356. This publication was made possible by NPRP Grant No. 9-174-2-092 from the Qatar National Research Fund (a member of the Qatar Foundation) (N.T.L.). NMR and MS measurements in this work were performed at the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). We thank Dr. Saman Shafaie for collecting high-resolution mass spectrometric data.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/9/12
Y1 - 2019/9/12
N2 - There has been increasing interest in the excited states of stable diradicals as means of manipulating their spin states for potential applications in quantum information science (QIS). In this work, we examine a set of diradicals composed of two stable naphthalene-1,8:4,5-bis(dicarboximide) radical anions (NDI•-) bound either directly at their imide nitrogen atoms or through a series of benzene spacers resulting in diradicals with either singlet or triplet ground states. We use time-resolved near-UV, visible, near-IR, and mid-IR spectroscopy to show that the population in the singlet ground state can undergo photoinduced electron transfer upon excitation of one of the NDI•- radicals to produce the NDI0-NDI2- moiety, while the corresponding triplet population cannot. In particular, spectroscopy in the wavelength region 330-450 nm and in the energy range 1450-1750 cm-1 is critical to distinguishing the two populations. By varying the connectivity between the two radical anions, we vary both the sign and magnitude of the singlet-triplet energy splitting (2J) of the diradicals, thereby varying the proportion of singlet and triplet ground state populations that are detected optically. EPR spectroscopy provides corroborating evidence for the ground spin state of the diradicals. This result has implications for using photoexcitation to manipulate the spin states of diradicals for QIS applications.
AB - There has been increasing interest in the excited states of stable diradicals as means of manipulating their spin states for potential applications in quantum information science (QIS). In this work, we examine a set of diradicals composed of two stable naphthalene-1,8:4,5-bis(dicarboximide) radical anions (NDI•-) bound either directly at their imide nitrogen atoms or through a series of benzene spacers resulting in diradicals with either singlet or triplet ground states. We use time-resolved near-UV, visible, near-IR, and mid-IR spectroscopy to show that the population in the singlet ground state can undergo photoinduced electron transfer upon excitation of one of the NDI•- radicals to produce the NDI0-NDI2- moiety, while the corresponding triplet population cannot. In particular, spectroscopy in the wavelength region 330-450 nm and in the energy range 1450-1750 cm-1 is critical to distinguishing the two populations. By varying the connectivity between the two radical anions, we vary both the sign and magnitude of the singlet-triplet energy splitting (2J) of the diradicals, thereby varying the proportion of singlet and triplet ground state populations that are detected optically. EPR spectroscopy provides corroborating evidence for the ground spin state of the diradicals. This result has implications for using photoexcitation to manipulate the spin states of diradicals for QIS applications.
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U2 - 10.1021/acs.jpcb.9b06303
DO - 10.1021/acs.jpcb.9b06303
M3 - Article
C2 - 31418270
AN - SCOPUS:85072134387
SN - 1520-6106
VL - 123
SP - 7731
EP - 7739
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 36
ER -