Programming electronic states in conductive metal-organic frame-works through crystallization-enabled proton management
Abstract
Conductive metal-organic frameworks (c-MOFs) are promising electronic materials, where electronic states critically determine electrical conductivity. However, achieving controllable modulation of these states during crystallization remains challenging. Existing approaches rely either on redesigning framework components or on introducing external dopants after crystallization, making electronic-state regulation dependent on structural modification or postsynthetic doping. Here, we demonstrate a crystallization-enabled in situ proton-management strategy for regulating the electronic state of c-MOFs. Using Co9HHTP4 as a model system, we show that distinct proton environments influence the balance between competing proton-coupled electron-transfer pathways during Co-O framework assembly while preserving the fundamental framework architecture. HNO3-mediated crystallization produces an electronic state consistent with enhanced electron retention within the Co-O framework and results in a single-crystal conductivity of 8.4 * 10-2 S cm-1, nearly four orders of magnitude higher than Co9HHTP4-NaOAc (1.7 * 10-5 S cm-1), together with a substantially reduced transport activation energy. Hall measurements further reveal a pronounced increase in carrier concentration for Co9HHTP4-HNO3, providing direct evidence that the enhanced conductivity is associated with a substantially increased carrier population. These results establish crystallization conditions as an active parameter for programming electronic states and charge transport in conductive frameworks.
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BibTeX
@misc{chen2026programming,
title = {{Programming electronic states in conductive metal-organic frame-works through crystallization-enabled proton management}},
author = {Hao Chen and Tongyang Zhao and Weishan Li and Jinkun Guo and Jia-Xiang Zhang and Ze-Fan Yao and Maojun Zheng and Jin-Hu Dou},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.08536},
eprint = {2610.08536},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.08536},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Programming electronic states in conductive metal-organic frame-works through crystallization-enabled proton management
AU - Hao Chen
AU - Tongyang Zhao
AU - Weishan Li
AU - Jinkun Guo
AU - Jia-Xiang Zhang
AU - Ze-Fan Yao
AU - Maojun Zheng
AU - Jin-Hu Dou
PY - 2026
DA - 2026/10/06
PB - arXiv
DO - 10.48550/arxiv.2610.08536
UR - https://arxiv.org/abs/2610.08536
AB - Conductive metal-organic frameworks (c-MOFs) are promising electronic materials, where electronic states critically determine electrical conductivity. However, achieving controllable modulation of these states during crystallization remains challenging. Existing approaches rely either on redesigning framework components or on introducing external dopants after crystallization, making electronic-state regulation dependent on structural modification or postsynthetic doping. Here, we demonstrate a crystallization-enabled in situ proton-management strategy for regulating the electronic state of c-MOFs. Using Co9HHTP4 as a model system, we show that distinct proton environments influence the balance between competing proton-coupled electron-transfer pathways during Co-O framework assembly while preserving the fundamental framework architecture. HNO3-mediated crystallization produces an electronic state consistent with enhanced electron retention within the Co-O framework and results in a single-crystal conductivity of 8.4 * 10-2 S cm-1, nearly four orders of magnitude higher than Co9HHTP4-NaOAc (1.7 * 10-5 S cm-1), together with a substantially reduced transport activation energy. Hall measurements further reveal a pronounced increase in carrier concentration for Co9HHTP4-HNO3, providing direct evidence that the enhanced conductivity is associated with a substantially increased carrier population. These results establish crystallization conditions as an active parameter for programming electronic states and charge transport in conductive frameworks.
ER -