Superior Charge Transport in Ni-Diamine Conductive MOFs

Jiande Wang; Tianyang Chen; Mingyu Jeon; Julius J. Oppenheim; Bowen Tan; Jihan Kim; Mircea Dincă

doi:10.1021/jacs.4c06935

Superior Charge Transport in Ni-Diamine Conductive MOFs

Jiande Wang
, Tianyang Chen
, Mingyu Jeon
, Julius J. Oppenheim
, Bowen Tan
, Jihan Kim
, Mircea Dincă

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

Two-dimensional conductive metal-organic frameworks (2D cMOFs) are an emerging class of crystalline van der Waals layered materials with tunable porosity and high electrical conductivity. They have been used in a variety of applications, such as energy storage and conversion, chemiresistive sensing, and quantum information. Although designing new conductive 2D cMOFs and studying their composition/structure-property relationships have attracted significant attention, there are still very few examples of 2D cMOFs that exhibit room-temperature electrical conductivity above 1 S cm^-1, the value exhibited by activated carbon, a well-known porous and conductive material that serves in myriad applications. When such high conductivities are achieved, Ni-diamine linkages are often involved, yet Ni-diamine MOFs remain difficult to access. Here, we report two new 2D cMOFs made through ortho-diamine connections: M₃(HITT)₂ (M = Ni, Cu; HITT = 2,3,7,8,12,13-hexaiminotetraazanaphthotetraphene). The electrical conductivity of Ni₃(HITT)₂ reaches 4.5 S cm^-1 at 298 K, whereas the conductivity of Cu₃(HITT)₂ spans from 0.05 (2Cu⁺Cu²⁺) to 10^-6 (3Cu²⁺) upon air oxidation, much lower than that of Ni₃(HITT)₂. Spectroscopic analysis reveals that Ni₃(HITT)₂ exhibits significantly stronger in-plane π-d conjugation and higher density of charge carriers compared to Cu₃(HITT)₂, accounting for the higher electrical conductivity of Ni₃(HITT)₂. Cu²⁺/Cu⁺ mixed valency modulates the energy level and carrier density of Cu₃(HITT)₂, allowing for a variation of electrical conductivity over 4 orders of magnitude. This work provides a deeper understanding of the influence of metal nodes on electrical conductivity and confirms ortho-diamine linkers as privileged among ligands for 2D cMOFs.

Original language	English (US)
Pages (from-to)	20500-20507
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	146
Issue number	29
DOIs	https://doi.org/10.1021/jacs.4c06935
State	Published - Jul 24 2024
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.4c06935

Cite this

@article{a4ffa75c131f45c293799e3bef774b9e,

title = "Superior Charge Transport in Ni-Diamine Conductive MOFs",

abstract = "Two-dimensional conductive metal-organic frameworks (2D cMOFs) are an emerging class of crystalline van der Waals layered materials with tunable porosity and high electrical conductivity. They have been used in a variety of applications, such as energy storage and conversion, chemiresistive sensing, and quantum information. Although designing new conductive 2D cMOFs and studying their composition/structure-property relationships have attracted significant attention, there are still very few examples of 2D cMOFs that exhibit room-temperature electrical conductivity above 1 S cm-1, the value exhibited by activated carbon, a well-known porous and conductive material that serves in myriad applications. When such high conductivities are achieved, Ni-diamine linkages are often involved, yet Ni-diamine MOFs remain difficult to access. Here, we report two new 2D cMOFs made through ortho-diamine connections: M3(HITT)2 (M = Ni, Cu; HITT = 2,3,7,8,12,13-hexaiminotetraazanaphthotetraphene). The electrical conductivity of Ni3(HITT)2 reaches 4.5 S cm-1 at 298 K, whereas the conductivity of Cu3(HITT)2 spans from 0.05 (2Cu+Cu2+) to 10-6 (3Cu2+) upon air oxidation, much lower than that of Ni3(HITT)2. Spectroscopic analysis reveals that Ni3(HITT)2 exhibits significantly stronger in-plane π-d conjugation and higher density of charge carriers compared to Cu3(HITT)2, accounting for the higher electrical conductivity of Ni3(HITT)2. Cu2+/Cu+ mixed valency modulates the energy level and carrier density of Cu3(HITT)2, allowing for a variation of electrical conductivity over 4 orders of magnitude. This work provides a deeper understanding of the influence of metal nodes on electrical conductivity and confirms ortho-diamine linkers as privileged among ligands for 2D cMOFs.",

author = "Jiande Wang and Tianyang Chen and Mingyu Jeon and Oppenheim, \{Julius J.\} and Bowen Tan and Jihan Kim and Mircea Dinc{\u a}",

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doi = "10.1021/jacs.4c06935",

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T1 - Superior Charge Transport in Ni-Diamine Conductive MOFs

AU - Wang, Jiande

AU - Chen, Tianyang

AU - Jeon, Mingyu

AU - Oppenheim, Julius J.

AU - Tan, Bowen

AU - Kim, Jihan

AU - Dincă, Mircea

PY - 2024/7/24

Y1 - 2024/7/24

N2 - Two-dimensional conductive metal-organic frameworks (2D cMOFs) are an emerging class of crystalline van der Waals layered materials with tunable porosity and high electrical conductivity. They have been used in a variety of applications, such as energy storage and conversion, chemiresistive sensing, and quantum information. Although designing new conductive 2D cMOFs and studying their composition/structure-property relationships have attracted significant attention, there are still very few examples of 2D cMOFs that exhibit room-temperature electrical conductivity above 1 S cm-1, the value exhibited by activated carbon, a well-known porous and conductive material that serves in myriad applications. When such high conductivities are achieved, Ni-diamine linkages are often involved, yet Ni-diamine MOFs remain difficult to access. Here, we report two new 2D cMOFs made through ortho-diamine connections: M3(HITT)2 (M = Ni, Cu; HITT = 2,3,7,8,12,13-hexaiminotetraazanaphthotetraphene). The electrical conductivity of Ni3(HITT)2 reaches 4.5 S cm-1 at 298 K, whereas the conductivity of Cu3(HITT)2 spans from 0.05 (2Cu+Cu2+) to 10-6 (3Cu2+) upon air oxidation, much lower than that of Ni3(HITT)2. Spectroscopic analysis reveals that Ni3(HITT)2 exhibits significantly stronger in-plane π-d conjugation and higher density of charge carriers compared to Cu3(HITT)2, accounting for the higher electrical conductivity of Ni3(HITT)2. Cu2+/Cu+ mixed valency modulates the energy level and carrier density of Cu3(HITT)2, allowing for a variation of electrical conductivity over 4 orders of magnitude. This work provides a deeper understanding of the influence of metal nodes on electrical conductivity and confirms ortho-diamine linkers as privileged among ligands for 2D cMOFs.

AB - Two-dimensional conductive metal-organic frameworks (2D cMOFs) are an emerging class of crystalline van der Waals layered materials with tunable porosity and high electrical conductivity. They have been used in a variety of applications, such as energy storage and conversion, chemiresistive sensing, and quantum information. Although designing new conductive 2D cMOFs and studying their composition/structure-property relationships have attracted significant attention, there are still very few examples of 2D cMOFs that exhibit room-temperature electrical conductivity above 1 S cm-1, the value exhibited by activated carbon, a well-known porous and conductive material that serves in myriad applications. When such high conductivities are achieved, Ni-diamine linkages are often involved, yet Ni-diamine MOFs remain difficult to access. Here, we report two new 2D cMOFs made through ortho-diamine connections: M3(HITT)2 (M = Ni, Cu; HITT = 2,3,7,8,12,13-hexaiminotetraazanaphthotetraphene). The electrical conductivity of Ni3(HITT)2 reaches 4.5 S cm-1 at 298 K, whereas the conductivity of Cu3(HITT)2 spans from 0.05 (2Cu+Cu2+) to 10-6 (3Cu2+) upon air oxidation, much lower than that of Ni3(HITT)2. Spectroscopic analysis reveals that Ni3(HITT)2 exhibits significantly stronger in-plane π-d conjugation and higher density of charge carriers compared to Cu3(HITT)2, accounting for the higher electrical conductivity of Ni3(HITT)2. Cu2+/Cu+ mixed valency modulates the energy level and carrier density of Cu3(HITT)2, allowing for a variation of electrical conductivity over 4 orders of magnitude. This work provides a deeper understanding of the influence of metal nodes on electrical conductivity and confirms ortho-diamine linkers as privileged among ligands for 2D cMOFs.

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UR - https://www.scopus.com/pages/publications/85199422785#tab=citedBy

U2 - 10.1021/jacs.4c06935

DO - 10.1021/jacs.4c06935

M3 - Article

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AN - SCOPUS:85199422785

SN - 0002-7863

VL - 146

SP - 20500

EP - 20507

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 29

ER -

Superior Charge Transport in Ni-Diamine Conductive MOFs

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