TY - JOUR
T1 - Electron Hopping and Charge Separation within a Naphthalene-1,4:5,8-bis(dicarboximide) Chiral Covalent Organic Cage
AU - Šolomek, Tomáš
AU - Powers-Riggs, Natalia E.
AU - Wu, Yi Lin
AU - Young, Ryan M.
AU - Krzyaniak, Matthew D.
AU - Horwitz, Noah E.
AU - Wasielewski, Michael R.
N1 - Funding Information:
This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, DOE under grant no. DE-FG02-99ER14999. We thank Dr. Saman Shafaie for collecting high-resolution mass spectrometric data. T.S?. thanks the Swiss National Science Foundation for postdoctoral scholarship.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/3/8
Y1 - 2017/3/8
N2 - We present the stereoselective synthesis of a chiral covalent organic cage consisting of three redox-active naphthalene-1,4:5,8-bis(dicarboximide) (NDI) units by dynamic imine chemistry. Single crystal X-ray diffraction analysis shows that host-guest interactions and racemic cocrystallization allow for controlling the solid state structure. Electronic interactions between the NDI units probed by absorption and circular dichroism spectroscopies, electrochemistry and theoretical calculations are shown to be weak. Photoexcitation of NDI leads to intracage charge separation with a longer lifetime than observed in the corresponding monomeric NDI and dimeric NDI cyclophane imines. The EPR spectrum of the singly reduced cage shows that the electron is localized on a single NDI unit at ambient temperatures and transitions to rapid hopping among all three NDI units upon heating to 350 K. Dynamic covalent chemistry thus promises rapid access to covalent organic cages with well-defined architectures to study charge accumulation and electron transport phenomena.
AB - We present the stereoselective synthesis of a chiral covalent organic cage consisting of three redox-active naphthalene-1,4:5,8-bis(dicarboximide) (NDI) units by dynamic imine chemistry. Single crystal X-ray diffraction analysis shows that host-guest interactions and racemic cocrystallization allow for controlling the solid state structure. Electronic interactions between the NDI units probed by absorption and circular dichroism spectroscopies, electrochemistry and theoretical calculations are shown to be weak. Photoexcitation of NDI leads to intracage charge separation with a longer lifetime than observed in the corresponding monomeric NDI and dimeric NDI cyclophane imines. The EPR spectrum of the singly reduced cage shows that the electron is localized on a single NDI unit at ambient temperatures and transitions to rapid hopping among all three NDI units upon heating to 350 K. Dynamic covalent chemistry thus promises rapid access to covalent organic cages with well-defined architectures to study charge accumulation and electron transport phenomena.
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U2 - 10.1021/jacs.7b00233
DO - 10.1021/jacs.7b00233
M3 - Article
C2 - 28222595
AN - SCOPUS:85014709754
VL - 139
SP - 3348
EP - 3351
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 9
ER -