Electron Delocalization and Charge Mobility as a Function of Reduction in a Metal–Organic Framework

Author

Michael L. Aubrey
Brian M. Wiers
Sean C. Andrews
Tsuneaki Sakurai
Sebastian E. Reyes-Lillo
Samia M. Hamed
Chung-Jui Yu
Lucy E. Darago
Jarad A. Mason
Jin-Ook Baeg
Fernande R. Grandjean, Missouri University of Science and TechnologyFollow
Gary J. Long, Missouri University of Science and TechnologyFollow
Shu Seki
Jeffrey B. Neaton
Peidong Yang
Jeffrey R. LongFollow

Abstract

Conductive metal-organic frameworks are an emerging class of three-dimensional architectures with degrees of modularity, synthetic flexibility and structural predictability that are unprecedented in other porous materials. However, engendering long-range charge delocalization and establishing synthetic strategies that are broadly applicable to the diverse range of structures encountered for this class of materials remain challenging. Here, we report the synthesis of K_xFe₂(BDP)₃ (0 ≤ x ≤ 2; BDP²⁻ = 1,4-benzenedipyrazolate), which exhibits full charge delocalization within the parent framework and charge mobilities comparable to technologically relevant polymers and ceramics. Through a battery of spectroscopic methods, computational techniques and single-microcrystal field-effect transistor measurements, we demonstrate that fractional reduction of Fe₂(BDP)₃results in a metal-organic framework that displays a nearly 10,000-fold enhancement in conductivity along a single crystallographic axis. The attainment of such properties in a K_x Fe₂(BDP)₃ field-effect transistor represents the realization of a general synthetic strategy for the creation of new porous conductor-based devices.

Recommended Citation

M. L. Aubrey and B. M. Wiers and S. C. Andrews and T. Sakurai and S. E. Reyes-Lillo and S. M. Hamed and C. Yu and L. E. Darago and J. A. Mason and J. Baeg and F. R. Grandjean and G. J. Long and S. Seki and J. B. Neaton and P. Yang and J. R. Long, "Electron Delocalization and Charge Mobility as a Function of Reduction in a Metal–Organic Framework," Nature Materials, vol. 17, pp. 625 - 632, Nature Publishing Group, Jun 2018.

The definitive version is available at https://doi.org/10.1038/s41563-018-0098-1

Department(s)

Chemistry

Research Center/Lab(s)

Center for High Performance Computing Research

International Standard Serial Number (ISSN)

1476-1122; 1476-4660

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2018 Nature Publishing Group. All rights reserved.

Publication Date

01 Jun 2018