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

Research output: Contribution to journalArticle

33 Citations (Scopus)

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 KxFe2(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)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 KxFe2(BDP)3 field-effect transistor represents the realization of a general synthetic strategy for the creation of new porous conductor-based devices.

Original languageEnglish
Pages (from-to)1-8
Number of pages8
JournalNature Materials
DOIs
Publication statusAccepted/In press - 4 Jun 2018

Fingerprint

Field effect transistors
field effect transistors
modularity
Microcrystals
Electrons
microcrystals
porous materials
Computational methods
Porous materials
electric batteries
emerging
flexibility
Polymers
electrons
conductors
ceramics
conductivity
augmentation
polymers
synthesis

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanics of Materials
  • Mechanical Engineering

Cite this

Aubrey, Michael L. ; Wiers, Brian M. ; Andrews, Sean C. ; Sakurai, Tsuneaki ; Reyes-Lillo, Sebastian E. ; Hamed, Samia M. ; Yu, Chung Jui ; Darago, Lucy E. ; Mason, Jarad A. ; Baeg, Jin Ook ; Grandjean, Fernande ; Long, Gary J. ; Seki, Shu ; Neaton, Jeffrey B. ; Yang, Peidong ; Long, Jeffrey R. / Electron delocalization and charge mobility as a function of reduction in a metal–organic framework. In: Nature Materials. 2018 ; pp. 1-8.
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Aubrey, ML, Wiers, BM, Andrews, SC, Sakurai, T, Reyes-Lillo, SE, Hamed, SM, Yu, CJ, Darago, LE, Mason, JA, Baeg, JO, Grandjean, F, Long, GJ, Seki, S, Neaton, JB, Yang, P & Long, JR 2018, 'Electron delocalization and charge mobility as a function of reduction in a metal–organic framework', Nature Materials, pp. 1-8. https://doi.org/10.1038/s41563-018-0098-1

Electron delocalization and charge mobility as a function of reduction in a metal–organic framework. / Aubrey, Michael L.; Wiers, Brian M.; Andrews, Sean C.; Sakurai, Tsuneaki; Reyes-Lillo, Sebastian E.; Hamed, Samia M.; Yu, Chung Jui; Darago, Lucy E.; Mason, Jarad A.; Baeg, Jin Ook; Grandjean, Fernande; Long, Gary J.; Seki, Shu; Neaton, Jeffrey B.; Yang, Peidong; Long, Jeffrey R.

In: Nature Materials, 04.06.2018, p. 1-8.

Research output: Contribution to journalArticle

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AU - Aubrey, Michael L.

AU - Wiers, Brian M.

AU - Andrews, Sean C.

AU - Sakurai, Tsuneaki

AU - Reyes-Lillo, Sebastian E.

AU - Hamed, Samia M.

AU - Yu, Chung Jui

AU - Darago, Lucy E.

AU - Mason, Jarad A.

AU - Baeg, Jin Ook

AU - Grandjean, Fernande

AU - Long, Gary J.

AU - Seki, Shu

AU - Neaton, Jeffrey B.

AU - Yang, Peidong

AU - Long, Jeffrey R.

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Y1 - 2018/6/4

N2 - 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 KxFe2(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)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 KxFe2(BDP)3 field-effect transistor represents the realization of a general synthetic strategy for the creation of new porous conductor-based devices.

AB - 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 KxFe2(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)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 KxFe2(BDP)3 field-effect transistor represents the realization of a general synthetic strategy for the creation of new porous conductor-based devices.

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