Unraveling the Semiconducting/Metallic Discrepancy in Ni3(HITP)2

Foster, Michael E.; Sohlberg, Karl; Allendorf, Mark D.; Talin, A. Alec

doi:10.1021/acs.jpclett.7b03140

Unraveling the Semiconducting/Metallic Discrepancy in Ni₃(HITP)₂

Journal Article · Wed Jan 10 00:00:00 EST 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b03140· OSTI ID:1421638

^[1]; Sohlberg, Karl ^[2]; Allendorf, Mark D. ^[1]; ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Drexel Univ., Philadelphia, PA (United States)

Here, Ni₃(2,3,6,7,10,11-hexaiminotriphenylene)₂ is a π-stacked layered metal–organic framework material with extended π-conjugation that is analogous to graphene. Published experimental results indicate that the material is semiconducting, but all theoretical studies to date predict the bulk material to be metallic. Given that previous experimental work was carried out on specimens containing complex nanocrystalline microstructures and the tendency for internal interfaces to introduce transport barriers, we apply DFT to investigate the influence of internal interface defects on the electronic structure of Ni₃(HITP)₂. The results show that interface defects can introduce a transport barrier by breaking the π-conjugation and/or decreasing the dispersion of the electronic bands near the Fermi level. We demonstrate that the presence of defects can open a small gap, in the range of 15–200 meV, which is consistent with the experimentally inferred hopping barrier.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1421638

Report Number(s):: SAND--2017-12553J; 658910

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 3 Vol. 9; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal–Organic Frameworks Rubio‐Giménez, Víctor; Almora‐Barrios, Neyvis; Escorcia‐Ariza, Garin Angewandte Chemie, Vol. 130, Issue 46 https://doi.org/10.1002/ange.201808242	journal	October 2018
Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal–Organic Frameworks Rubio‐Giménez, Víctor; Almora‐Barrios, Neyvis; Escorcia‐Ariza, Garin Angewandte Chemie International Edition, Vol. 57, Issue 46 https://doi.org/10.1002/anie.201808242	journal	November 2018
A Highly Conductive MOF of Graphene Analogue Ni ₃ (HITP) ₂ as a Sulfur Host for High‐Performance Lithium–Sulfur Batteries Cai, Dong; Lu, Mengjie; Li, La Small, Vol. 15, Issue 44 https://doi.org/10.1002/smll.201902605	journal	September 2019
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Proximity Effect in Crystalline Framework Materials: Stacking‐Induced Functionality in MOFs and COFs Kuc, Agnieszka; Springer, Maximilian A.; Batra, Kamal Wiley-VCH Verlag https://doi.org/10.5445/ir/1000105891	text	January 2020

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