Precise tuning of interlayer electronic coupling in layered conductive metal-organic frameworks

Yang Lu; Yingying Zhang; Chi Yuan Yang; Sergio Revuelta; Haoyuan Qi; Chuanhui Huang; Wenlong Jin; Zichao Li; Victor Vega-Mayoral; Yannan Liu; Xing Huang; Darius Pohl; Miroslav Položij; Shengqiang Zhou; Enrique Cánovas; Thomas Heine; Simone Fabiano; Xinliang Feng; Renhao Dong

doi:10.1038/s41467-022-34820-6

Precise tuning of interlayer electronic coupling in layered conductive metal-organic frameworks

Yang Lu, Yingying Zhang, Chi Yuan Yang, Sergio Revuelta, Haoyuan Qi, Chuanhui Huang, Wenlong Jin, Zichao Li, Victor Vega-Mayoral, Yannan Liu, Xing Huang, Darius Pohl, Miroslav Položij, Shengqiang Zhou, Enrique Cánovas, Thomas Heine, Simone Fabiano, Xinliang Feng, Renhao Dong

Department of Chemistry

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

Abstract

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interests for (opto)-electronics and spintronics. They generally consist of van der Waals stacked layers and exhibit layer-depended electronic properties. While considerable efforts have been made to regulate the charge transport within a layer, precise control of electronic coupling between layers has not yet been achieved. Herein, we report a strategy to precisely tune interlayer charge transport in 2D c-MOFs via side-chain induced control of the layer spacing. We design hexaiminotriindole ligands allowing programmed functionalization with tailored alkyl chains (HATI_CX, X = 1,3,4; X refers to the carbon numbers of the alkyl chains) for the synthesis of semiconducting Ni₃(HATI_CX)₂. The layer spacing of these MOFs can be precisely varied from 3.40 to 3.70 Å, leading to widened band gap, suppressed carrier mobilities, and significant improvement of the Seebeck coefficient. With this demonstration, we further achieve a record-high thermoelectric power factor of 68 ± 3 nW m⁻¹ K⁻² in Ni₃(HATI_C3)₂, superior to the reported holes-dominated MOFs.

Original language	English
Article number	7240
Journal	Nature communications
Volume	13
Issue number	1
DOIs	https://doi.org/10.1038/s41467-022-34820-6
Publication status	Published - 2022 Dec

Bibliographical note

Funding Information:
The authors acknowledge cfaed and Dresden Center for Nano-analysis (DCN) at TUD. This work is financially supported by ERC starting grant (FC2DMOF, No. 852909), EU Graphene Flagship (Core3, No. 881603), ERC Consolidator Grant (T2DCP), DFG projects (CRC-1415, No. 417590517; SPP-1928, COORNET), H2020-MSCA-ITN (ULTIMATE, No. 813036), EMPIR-20FUN03-COMET, H2020-FETOPEN (PROGENY, 899205) as well as the German Science Council and Center of Advancing Electronics Dresden (cfaed). R.D. thanks Taishan Scholars Program of Shandong Province (tsqn201909047) and the National Natural Science Foundation of China (22272092). E.C. acknowledges MCIN/AEI grant PID2019-107808RA-I00 and Comunidad de Madrid grants 2021-5A/AMB-20942 & P2018/NMT-451. S.F. acknowledges support from the Swedish Research Council (2020-03243) and the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU 2009-00971). Y.Z. acknowledges China Scholarship Council. Y.L. and Y.Z. acknowledge ZIH Dresden for computer time.

Funding Information:
The authors acknowledge cfaed and Dresden Center for Nano-analysis (DCN) at TUD. This work is financially supported by ERC starting grant (FC2DMOF, No. 852909), EU Graphene Flagship (Core3, No. 881603), ERC Consolidator Grant (T2DCP), DFG projects (CRC-1415, No. 417590517; SPP-1928, COORNET), H2020-MSCA-ITN (ULTIMATE, No. 813036), EMPIR-20FUN03-COMET, H2020-FETOPEN (PROGENY, 899205) as well as the German Science Council and Center of Advancing Electronics Dresden (cfaed). R.D. thanks Taishan Scholars Program of Shandong Province (tsqn201909047) and the National Natural Science Foundation of China (22272092). E.C. acknowledges MCIN/AEI grant PID2019-107808RA-I00 and Comunidad de Madrid grants 2021-5A/AMB-20942 & P2018/NMT-451. S.F. acknowledges support from the Swedish Research Council (2020-03243) and the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU 2009-00971). Y.Z. acknowledges China Scholarship Council. Y.L. and Y.Z. acknowledge ZIH Dresden for computer time.

Publisher Copyright:
© 2022, The Author(s).

All Science Journal Classification (ASJC) codes

Chemistry(all)
Biochemistry, Genetics and Molecular Biology(all)
General
Physics and Astronomy(all)

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10.1038/s41467-022-34820-6

Cite this

Lu, Y., Zhang, Y., Yang, C. Y., Revuelta, S., Qi, H., Huang, C., Jin, W., Li, Z., Vega-Mayoral, V., Liu, Y., Huang, X., Pohl, D., Položij, M., Zhou, S., Cánovas, E., Heine, T., Fabiano, S., Feng, X., & Dong, R. (2022). Precise tuning of interlayer electronic coupling in layered conductive metal-organic frameworks. Nature communications, 13(1), [7240]. https://doi.org/10.1038/s41467-022-34820-6

@article{5b639e88da4d41cd84cda2b6de894b07,

title = "Precise tuning of interlayer electronic coupling in layered conductive metal-organic frameworks",

abstract = "Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interests for (opto)-electronics and spintronics. They generally consist of van der Waals stacked layers and exhibit layer-depended electronic properties. While considerable efforts have been made to regulate the charge transport within a layer, precise control of electronic coupling between layers has not yet been achieved. Herein, we report a strategy to precisely tune interlayer charge transport in 2D c-MOFs via side-chain induced control of the layer spacing. We design hexaiminotriindole ligands allowing programmed functionalization with tailored alkyl chains (HATI_CX, X = 1,3,4; X refers to the carbon numbers of the alkyl chains) for the synthesis of semiconducting Ni3(HATI_CX)2. The layer spacing of these MOFs can be precisely varied from 3.40 to 3.70 {\AA}, leading to widened band gap, suppressed carrier mobilities, and significant improvement of the Seebeck coefficient. With this demonstration, we further achieve a record-high thermoelectric power factor of 68 ± 3 nW m−1 K−2 in Ni3(HATI_C3)2, superior to the reported holes-dominated MOFs.",

author = "Yang Lu and Yingying Zhang and Yang, {Chi Yuan} and Sergio Revuelta and Haoyuan Qi and Chuanhui Huang and Wenlong Jin and Zichao Li and Victor Vega-Mayoral and Yannan Liu and Xing Huang and Darius Pohl and Miroslav Polo{\v z}ij and Shengqiang Zhou and Enrique C{\'a}novas and Thomas Heine and Simone Fabiano and Xinliang Feng and Renhao Dong",

note = "Funding Information: The authors acknowledge cfaed and Dresden Center for Nano-analysis (DCN) at TUD. This work is financially supported by ERC starting grant (FC2DMOF, No. 852909), EU Graphene Flagship (Core3, No. 881603), ERC Consolidator Grant (T2DCP), DFG projects (CRC-1415, No. 417590517; SPP-1928, COORNET), H2020-MSCA-ITN (ULTIMATE, No. 813036), EMPIR-20FUN03-COMET, H2020-FETOPEN (PROGENY, 899205) as well as the German Science Council and Center of Advancing Electronics Dresden (cfaed). R.D. thanks Taishan Scholars Program of Shandong Province (tsqn201909047) and the National Natural Science Foundation of China (22272092). E.C. acknowledges MCIN/AEI grant PID2019-107808RA-I00 and Comunidad de Madrid grants 2021-5A/AMB-20942 & P2018/NMT-451. S.F. acknowledges support from the Swedish Research Council (2020-03243) and the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Link{\"o}ping University (Faculty Grant SFO-Mat-LiU 2009-00971). Y.Z. acknowledges China Scholarship Council. Y.L. and Y.Z. acknowledge ZIH Dresden for computer time. Funding Information: The authors acknowledge cfaed and Dresden Center for Nano-analysis (DCN) at TUD. This work is financially supported by ERC starting grant (FC2DMOF, No. 852909), EU Graphene Flagship (Core3, No. 881603), ERC Consolidator Grant (T2DCP), DFG projects (CRC-1415, No. 417590517; SPP-1928, COORNET), H2020-MSCA-ITN (ULTIMATE, No. 813036), EMPIR-20FUN03-COMET, H2020-FETOPEN (PROGENY, 899205) as well as the German Science Council and Center of Advancing Electronics Dresden (cfaed). R.D. thanks Taishan Scholars Program of Shandong Province (tsqn201909047) and the National Natural Science Foundation of China (22272092). E.C. acknowledges MCIN/AEI grant PID2019-107808RA-I00 and Comunidad de Madrid grants 2021-5A/AMB-20942 & P2018/NMT-451. S.F. acknowledges support from the Swedish Research Council (2020-03243) and the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Link{\"o}ping University (Faculty Grant SFO-Mat-LiU 2009-00971). Y.Z. acknowledges China Scholarship Council. Y.L. and Y.Z. acknowledge ZIH Dresden for computer time. Publisher Copyright: {\textcopyright} 2022, The Author(s).",

year = "2022",

month = dec,

doi = "10.1038/s41467-022-34820-6",

language = "English",

volume = "13",

journal = "Nature Communications",

issn = "2041-1723",

publisher = "Nature Publishing Group",

number = "1",

}

Lu, Y, Zhang, Y, Yang, CY, Revuelta, S, Qi, H, Huang, C, Jin, W, Li, Z, Vega-Mayoral, V, Liu, Y, Huang, X, Pohl, D, Položij, M, Zhou, S, Cánovas, E, Heine, T, Fabiano, S, Feng, X & Dong, R 2022, 'Precise tuning of interlayer electronic coupling in layered conductive metal-organic frameworks', Nature communications, vol. 13, no. 1, 7240. https://doi.org/10.1038/s41467-022-34820-6

TY - JOUR

T1 - Precise tuning of interlayer electronic coupling in layered conductive metal-organic frameworks

AU - Lu, Yang

AU - Zhang, Yingying

AU - Yang, Chi Yuan

AU - Revuelta, Sergio

AU - Qi, Haoyuan

AU - Huang, Chuanhui

AU - Jin, Wenlong

AU - Li, Zichao

AU - Vega-Mayoral, Victor

AU - Liu, Yannan

AU - Huang, Xing

AU - Pohl, Darius

AU - Položij, Miroslav

AU - Zhou, Shengqiang

AU - Cánovas, Enrique

AU - Heine, Thomas

AU - Fabiano, Simone

AU - Feng, Xinliang

AU - Dong, Renhao

N1 - Funding Information: The authors acknowledge cfaed and Dresden Center for Nano-analysis (DCN) at TUD. This work is financially supported by ERC starting grant (FC2DMOF, No. 852909), EU Graphene Flagship (Core3, No. 881603), ERC Consolidator Grant (T2DCP), DFG projects (CRC-1415, No. 417590517; SPP-1928, COORNET), H2020-MSCA-ITN (ULTIMATE, No. 813036), EMPIR-20FUN03-COMET, H2020-FETOPEN (PROGENY, 899205) as well as the German Science Council and Center of Advancing Electronics Dresden (cfaed). R.D. thanks Taishan Scholars Program of Shandong Province (tsqn201909047) and the National Natural Science Foundation of China (22272092). E.C. acknowledges MCIN/AEI grant PID2019-107808RA-I00 and Comunidad de Madrid grants 2021-5A/AMB-20942 & P2018/NMT-451. S.F. acknowledges support from the Swedish Research Council (2020-03243) and the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU 2009-00971). Y.Z. acknowledges China Scholarship Council. Y.L. and Y.Z. acknowledge ZIH Dresden for computer time. Funding Information: The authors acknowledge cfaed and Dresden Center for Nano-analysis (DCN) at TUD. This work is financially supported by ERC starting grant (FC2DMOF, No. 852909), EU Graphene Flagship (Core3, No. 881603), ERC Consolidator Grant (T2DCP), DFG projects (CRC-1415, No. 417590517; SPP-1928, COORNET), H2020-MSCA-ITN (ULTIMATE, No. 813036), EMPIR-20FUN03-COMET, H2020-FETOPEN (PROGENY, 899205) as well as the German Science Council and Center of Advancing Electronics Dresden (cfaed). R.D. thanks Taishan Scholars Program of Shandong Province (tsqn201909047) and the National Natural Science Foundation of China (22272092). E.C. acknowledges MCIN/AEI grant PID2019-107808RA-I00 and Comunidad de Madrid grants 2021-5A/AMB-20942 & P2018/NMT-451. S.F. acknowledges support from the Swedish Research Council (2020-03243) and the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU 2009-00971). Y.Z. acknowledges China Scholarship Council. Y.L. and Y.Z. acknowledge ZIH Dresden for computer time. Publisher Copyright: © 2022, The Author(s).

PY - 2022/12

Y1 - 2022/12

N2 - Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interests for (opto)-electronics and spintronics. They generally consist of van der Waals stacked layers and exhibit layer-depended electronic properties. While considerable efforts have been made to regulate the charge transport within a layer, precise control of electronic coupling between layers has not yet been achieved. Herein, we report a strategy to precisely tune interlayer charge transport in 2D c-MOFs via side-chain induced control of the layer spacing. We design hexaiminotriindole ligands allowing programmed functionalization with tailored alkyl chains (HATI_CX, X = 1,3,4; X refers to the carbon numbers of the alkyl chains) for the synthesis of semiconducting Ni3(HATI_CX)2. The layer spacing of these MOFs can be precisely varied from 3.40 to 3.70 Å, leading to widened band gap, suppressed carrier mobilities, and significant improvement of the Seebeck coefficient. With this demonstration, we further achieve a record-high thermoelectric power factor of 68 ± 3 nW m−1 K−2 in Ni3(HATI_C3)2, superior to the reported holes-dominated MOFs.

AB - Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interests for (opto)-electronics and spintronics. They generally consist of van der Waals stacked layers and exhibit layer-depended electronic properties. While considerable efforts have been made to regulate the charge transport within a layer, precise control of electronic coupling between layers has not yet been achieved. Herein, we report a strategy to precisely tune interlayer charge transport in 2D c-MOFs via side-chain induced control of the layer spacing. We design hexaiminotriindole ligands allowing programmed functionalization with tailored alkyl chains (HATI_CX, X = 1,3,4; X refers to the carbon numbers of the alkyl chains) for the synthesis of semiconducting Ni3(HATI_CX)2. The layer spacing of these MOFs can be precisely varied from 3.40 to 3.70 Å, leading to widened band gap, suppressed carrier mobilities, and significant improvement of the Seebeck coefficient. With this demonstration, we further achieve a record-high thermoelectric power factor of 68 ± 3 nW m−1 K−2 in Ni3(HATI_C3)2, superior to the reported holes-dominated MOFs.

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Precise tuning of interlayer electronic coupling in layered conductive metal-organic frameworks

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