Bulk conductivities; Chemical functionality; Fine tuning; Functionalized; Isostructural; Metalorganic frameworks (MOFs); Postfunctionalization; Reactive site; Symmetrics; Two-dimensional; Catalysis; Chemistry (all); Biochemistry; Colloid and Surface Chemistry; General Chemistry
Abstract :
[en] Two-dimensional electrically conducting metal-organic frameworks (2D-e-MOFs) have emerged as a class of highly promising functional materials for a wide range of applications. However, despite the significant recent advances in 2D-e-MOFs, developing systems that can be postsynthetically chemically functionalized, while also allowing fine-tuning of the transport properties, remains challenging. Herein, we report two isostructural 2D-e-MOFs: Ni3(HITAT)2 and Ni3(HITBim)2 based on two new 3-fold symmetric ligands: 2,3,7,8,12,13-hexaaminotriazatruxene (HATAT) and 2,3,8,9,14,15-hexaaminotribenzimidazole (HATBim), respectively, with reactive sites for postfunctionalization. Ni3(HITAT)2 and Ni3(HITBim)2 exhibit temperature-activated charge transport, with bulk conductivity values of 44 and 0.5 mS cm-1, respectively. Density functional theory analysis attributes the difference to disparities in the electron density distribution within the parent ligands: nitrogen-rich HATBim exhibits localized electron density and a notably lower lowest unoccupied molecular orbital (LUMO) energy relative to HATAT. Precise amounts of methanesulfonyl groups are covalently bonded to the N-H indole moiety within the Ni3(HITAT)2 framework, modulating the electrical conductivity by a factor of ∼20. These results provide a blueprint for the design of porous functional materials with tunable chemical functionality and electrical response.
Disciplines :
Chemistry
Author, co-author :
Apostol, Petru; Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université Catholique de Louvain, Louvain-la-Neuve B-1348, Belgium
Gali, Sai Manoj ; Université de Mons - UMONS > Faculté des Science > Service de Chimie des matériaux nouveaux
Su, Alice; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139-4307, United States
Tie, Da; Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université Catholique de Louvain, Louvain-la-Neuve B-1348, Belgium
Zhang, Yan; Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université Catholique de Louvain, Louvain-la-Neuve B-1348, Belgium
Pal, Shubhadeep; Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université Catholique de Louvain, Louvain-la-Neuve B-1348, Belgium
Lin, Xiaodong ; Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université Catholique de Louvain, Louvain-la-Neuve B-1348, Belgium
Bakuru, Vasudeva Rao; Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université Catholique de Louvain, Louvain-la-Neuve B-1348, Belgium
Rambabu, Darsi; Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université Catholique de Louvain, Louvain-la-Neuve B-1348, Belgium
Beljonne, David ; Université de Mons - UMONS > Faculté des Science > Service de Chimie des matériaux nouveaux
Dincă, Mircea ; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139-4307, United States
Vlad, Alexandru ; Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis, Université Catholique de Louvain, Louvain-la-Neuve B-1348, Belgium
Language :
English
Title :
Controlling Charge Transport in 2D Conductive MOFs─The Role of Nitrogen-Rich Ligands and Chemical Functionality.
R400 - Institut de Recherche en Science et Ingénierie des Matériaux Complexys
Funders :
U.S. Department of Energy European Commission Fonds De La Recherche Scientifique - FNRS European Commission Wallon Region
Funding text :
D.T. and Y.Z. acknowledge the China Scholarship Council for the PhD scholarship. A.V. is indebted to the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement no. 770870), as well as for the partial support from F.R.S.-FNRS through F.4552.21-P─MIS─CSA-LION grant. Research in the Dinca lab was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under award #DE-SC0023288. The computational resources in Mons are supported by the FNRS “Consortium des Equipements de Calcul Intensif–CECI” program grant no. 2.5020.11 and by the Walloon Region (ZENOBE Tier-1 supercomputer, under grant 1117545). X.L. acknowledges financial support from the Marie Skłodowska-Curie Actions (grant agreement no. 101064286) for his postdoctoral fellowship. S.M.G. and D.R. are Chargé de Recherche-FNRS, and DB is Research Director-FNRS.
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