G-quadruplex organic frameworks

Abstract

Two-dimensional covalent organic frameworks often π stack into crystalline solids that allow precise spatial positioning of molecular building blocks. Inspired by the hydrogen-bonded G-quadruplexes found frequently in guanine-rich DNA, here we show that this structural motif can be exploited to guide the self-assembly of naphthalene diimide and perylene diimide electron acceptors end-capped with two guanine electron donors into crystalline G-quadruplex-based organic frameworks, wherein the electron donors and acceptors form ordered, segregated π-stacked arrays. Time-resolved optical and electron paramagnetic resonance spectroscopies show that photogenerated holes and electrons in the frameworks have long lifetimes and display recombination kinetics typical of dissociated charge carriers. Moreover, the reduced acceptors form polarons in which the electron is shared over several molecules. The G-quadruplex frameworks also demonstrate potential as cathode materials in Li-ion batteries because of the favourable electron- and Li-ion-transporting capacity provided by the ordered rylene diimide arrays and G-quadruplex structures, respectively.

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Figure 1: Preparation of G-quadruplex organic frameworks.
Figure 2: Crystalline and porous G-quadruplex organic frameworks of G2NDI and G2PDI.
Figure 3: Femtosecond time-resolved transient-absorption spectra.
Figure 4: Time-resolved EPR spectra.
Figure 5: Comparison of CW-EPR spectra of reduced rylene diimides in the frameworks and in isolated molecules.
Figure 6: Electrochemical response and performance of a Li-ion battery using G2PDI as the cathode.

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Acknowledgements

This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Department of Energy (DOE) under grant no. DE-FG02-99ER14999 (M.R.W.). N.E.H. was supported in part by the Department of Energy Office of Science Graduate Fellowship Program (DOE SCGF), made possible in part by the American Recovery and Reinvestment Act of 2009, administered by ORISE-ORAU under contract no. DE-AC05-06OR23100. K.-S.C. and M.C.H. acknowledge the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the US DOE Office of Basic Energy Sciences (Award No. DE-AC02-06CH11357), for Li-ion battery fabrication and testing. The computational work was supported by the National Science Foundation (NSF) under grant no. DMR-1334928 (R.Q.S.). J.T.H. and O.K.F. acknowledge support from the US DOE Office of Science, Office of Basic Energy Sciences (grant no. DE-FG02-87ER13808) and Northwestern University. This work made use of the J.B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of Northwestern University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205). This work made use of the EPIC facility of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN.

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Y.-L.W. and M.R.W. planned and directed the project. Y.-L.W., N.E.H., N.S.L., K.-S.C., L.M, and T.C.W. prepared the materials, performed the structural characterization and carried out measurements and data analysis. D.A.G.-G. developed the structural models and carried out the simulations. All the authors contributed to the analysis of the results and the writing of the manuscript.

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Correspondence to Yi-Lin Wu or Michael R. Wasielewski.

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Wu, Y., Horwitz, N., Chen, K. et al. G-quadruplex organic frameworks. Nature Chem 9, 466–472 (2017). https://doi.org/10.1038/nchem.2689

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