Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two‐Dimensional Metal–Organic Frameworks

Wang, Denan; Ostresh, Sarah; Streater, Daniel; He, Peilei; Nyakuchena, James; Ma, Qiushi; Zhang, Xiaoyi; Neu, Jens; Brudvig, Gary W.; Huang, Jier

doi:10.1002/ange.202309505

Title: Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two‐Dimensional Metal–Organic Frameworks

Journal Article · 08 November 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202309505 · OSTI ID:2205252

Wang, Denan ^[1]; Ostresh, Sarah ^[2]; Streater, Daniel ^[3]; He, Peilei ^[3]; Nyakuchena, James ^[3]; Ma, Qiushi ^[1]; Zhang, Xiaoyi ^[4]; Neu, Jens ^[5]; Brudvig, Gary W. ^[2];

^[1]

Department of Chemistry, Schiller Institute for Integrated Science and Society Boston College Chestnut Hill MA 02467 USA
Department of Chemistry and Yale Energy Science Institute Yale University New Haven CT 06520–8107 USA
Department of Chemistry Marquette University Milwaukee WI 53201 USA
X-ray Science Division Argonne National Laboratory Argonne IL 60349 USA
Department of Physics University of North Texas Denton TX 76205 USA

Abstract Metal–organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M−HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11‐hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time‐resolved terahertz spectroscopy, optical transient absorption spectroscopy, X‐ray transient absorption spectroscopy, and density functional theory (DFT) calculations. We identify the through‐space hole transport mechanism through the interlayer sheet π–π interaction, where photoinduced hole state resides in HHTP ligand and electronic state is localized at the metal center. Moreover, the photoconductivity of the Cu−HHTP MOF is found to be 65.5 S m ⁻¹ , which represents the record high photoconductivity for porous MOF materials based on catecholate ligands.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0024049

OSTI ID:: 2205252

Alternate ID(s):: OSTI ID: 2205253

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 50 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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