Electron delocalization and charge mobility as a function of reduction in a metal-organic framework

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 Grandjean; Gary J Long; Shu Seki; Jeffrey B Neaton; Peidong Yang; Jeffrey R Long

doi:10.1038/s41563-018-0098-1

Electron delocalization and charge mobility as a function of reduction in a metal-organic framework

Nat Mater. 2018 Jul;17(7):625-632. doi: 10.1038/s41563-018-0098-1. Epub 2018 Jun 4.

Authors

Michael L Aubrey¹, Brian M Wiers¹, Sean C Andrews^{1

2}, Tsuneaki Sakurai³, Sebastian E Reyes-Lillo^{4

5

6}, Samia M Hamed^{1

4

5

7}, Chung-Jui Yu¹, Lucy E Darago¹, Jarad A Mason¹, Jin-Ook Baeg⁸, Fernande Grandjean⁹, Gary J Long¹⁰, Shu Seki³, Jeffrey B Neaton^{4

5

7}, Peidong Yang^{11

12

13

14}, Jeffrey R Long^{15

16

17}

Affiliations

¹ Department of Chemistry, University of California, Berkeley, CA, USA.
² Corporate Research & Development, Qualcomm Technology Inc, San Diego, CA, USA.
³ Department of Molecular Engineering, Kyoto University, Kyoto, Japan.
⁴ Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
⁵ Department of Physics, University of California, Berkeley, CA, USA.
⁶ Departamento de Ciencias Fisicas, Universidad Andres Bello, Santiago, Chile.
⁷ Kavli Energy NanoSciences Institute at Berkeley, Berkeley, CA, USA.
⁸ Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology, Daejeon, Republic of Korea.
⁹ Department of Chemistry, Missouri University of Science and Technology, University of Missouri, Rolla, MO, USA.
¹⁰ Department of Chemistry, Missouri University of Science and Technology, University of Missouri, Rolla, MO, USA. glong@mst.edu.
¹¹ Department of Chemistry, University of California, Berkeley, CA, USA. p_yang@berkeley.edu.
¹² Kavli Energy NanoSciences Institute at Berkeley, Berkeley, CA, USA. p_yang@berkeley.edu.
¹³ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. p_yang@berkeley.edu.
¹⁴ Department of Materials Science and Engineering, University of California, Berkeley, CA, USA. p_yang@berkeley.edu.
¹⁵ Department of Chemistry, University of California, Berkeley, CA, USA. jrlong@berkeley.edu.
¹⁶ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. jrlong@berkeley.edu.
¹⁷ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, USA. jrlong@berkeley.edu.

PMID: 29867169
DOI: 10.1038/s41563-018-0098-1

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 _x Fe₂(BDP)₃ (0 ≤ x ≤ 2; BDP^2- = 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)₃ results 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.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.