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Title: Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks

Abstract

Isostructural metal-organic frameworks (MOFs) M2(TTFTB) (M = Mn, Co, Zn, and Cd; H4TTFTB = tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single-crystal conductivities and the shortest S···S interaction defined by neighboring TTF cores, which inversely correlates with the ionic radius of the metal ions. The larger cations cause a pinching of the S···S contact, which is responsible for better orbital overlap between pz orbitals on neighboring S and C atoms. Density functional theory calculations show that these orbitals are critically involved in the valence band of these materials, such that modulation of the S···S distance has an important effect on band dispersion and, implicitly, on the conductivity. The Cd analogue, with the largest cation and shortest S···S contact, shows the largest electrical conductivity, σ = 2.86 (±0.53) × 10-4 S/cm, which is also among the highest in microporous MOFs. These results describe the first demonstration of tunable intrinsic electrical conductivity in this class of materials and serve as a blueprint for controlling charge transport in MOFs with π-stacked motifs.

Authors:
 [1];  [1];  [1];  [2];  [2];  [1];  [1]
  1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States
  2. Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Excitonics (CE)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1170238
Alternate Identifier(s):
OSTI ID: 1385577
Grant/Contract Number:  
SC0001088; SC0006937
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 5; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; solar (photovoltaic), solid state lighting, photosynthesis (natural and artificial), charge transport, optics, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Park, Sarah S., Hontz, Eric R., Sun, Lei, Hendon, Christopher H., Walsh, Aron, Van Voorhis, Troy, and Dincă, Mircea. Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks. United States: N. p., 2015. Web. doi:10.1021/ja512437u.
Park, Sarah S., Hontz, Eric R., Sun, Lei, Hendon, Christopher H., Walsh, Aron, Van Voorhis, Troy, & Dincă, Mircea. Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks. United States. https://doi.org/10.1021/ja512437u
Park, Sarah S., Hontz, Eric R., Sun, Lei, Hendon, Christopher H., Walsh, Aron, Van Voorhis, Troy, and Dincă, Mircea. Thu . "Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks". United States. https://doi.org/10.1021/ja512437u.
@article{osti_1170238,
title = {Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks},
author = {Park, Sarah S. and Hontz, Eric R. and Sun, Lei and Hendon, Christopher H. and Walsh, Aron and Van Voorhis, Troy and Dincă, Mircea},
abstractNote = {Isostructural metal-organic frameworks (MOFs) M2(TTFTB) (M = Mn, Co, Zn, and Cd; H4TTFTB = tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single-crystal conductivities and the shortest S···S interaction defined by neighboring TTF cores, which inversely correlates with the ionic radius of the metal ions. The larger cations cause a pinching of the S···S contact, which is responsible for better orbital overlap between pz orbitals on neighboring S and C atoms. Density functional theory calculations show that these orbitals are critically involved in the valence band of these materials, such that modulation of the S···S distance has an important effect on band dispersion and, implicitly, on the conductivity. The Cd analogue, with the largest cation and shortest S···S contact, shows the largest electrical conductivity, σ = 2.86 (±0.53) × 10-4 S/cm, which is also among the highest in microporous MOFs. These results describe the first demonstration of tunable intrinsic electrical conductivity in this class of materials and serve as a blueprint for controlling charge transport in MOFs with π-stacked motifs.},
doi = {10.1021/ja512437u},
journal = {Journal of the American Chemical Society},
number = 5,
volume = 137,
place = {United States},
year = {2015},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/ja512437u

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Cited by: 84 works
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Figures / Tables:

Figure 1 Figure 1: (a) Calculated band structure and projected density of states of Zn2(TTFTB). The work function, ϕ, and absolute energy scale are aligned to vacuum according to ref 20. The coordinates of the reciprocal space points are Γ = (0, 0, 0) and A = (0, 0, 1/2). Corresponding pictorialmore » representation of the valence band orbitals in Zn2(TTFTB) (b) and one of the TTF cores (c). Zn atoms and their coordination sphere are represented by black polyhedra. Gold, red, black, and white spheres represent S, O, C, and H atoms, respectively.« less

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