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Superior Charge Transport in Ni-Diamine Conductive MOFs.
Wang, Jiande; Chen, Tianyang; Jeon, Mingyu; Oppenheim, Julius J; Tan, Bowen; Kim, Jihan; Dinca, Mircea.
Afiliação
  • Wang J; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
  • Chen T; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
  • Jeon M; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
  • Oppenheim JJ; Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea.
  • Tan B; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
  • Kim J; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
  • Dinca M; Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea.
J Am Chem Soc ; 146(29): 20500-20507, 2024 Jul 24.
Article em En | MEDLINE | ID: mdl-39007301
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.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Ano de publicação: 2024 Tipo de documento: Article

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Ano de publicação: 2024 Tipo de documento: Article