发表机构
School of Physics and Astronomy, Shanghai Jiao Tong University; School of Materials Science and Engineering, Peking University; College of Chemistry and Molecular Engineering, Peking University（上海交通大学物理与天文学院; 北京大学材料科学与工程学院; 北京大学化学与分子工程学院）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本研究提出结晶驱动的原位质子管理策略，通过调控质子环境调节导电金属-有机框架的电子态，显著提升电导率，为电子材料设计提供新途径。
AI 中文摘要
导电金属-有机框架（c-MOFs）是有前景的电子材料，其中电子态关键地决定电导率。然而，在结晶过程中实现这些状态的可控调制仍然具有挑战性。现有方法要么依赖重新设计框架组分，要么在结晶后引入外部掺杂剂，使得电子态调控依赖于结构修饰或后合成掺杂。在此，我们展示了一种结晶驱动的原位质子管理策略，用于调控c-MOFs的电子态。以Co9HHTP4为模型体系，我们表明不同的质子环境在Co-O框架组装过程中影响竞争性质子耦合电子转移途径之间的平衡，同时保持基本框架架构。HNO3介导的结晶产生与Co-O框架内增强电子保留一致的电子态，并导致单晶电导率为8.4 * 10-2 S cm-1，比Co9HHTP4-NaOAc（1.7 * 10-5 S cm-1）高出近四个数量级，同时传输活化能显著降低。霍尔测量进一步揭示Co9HHTP4-HNO3的载流子浓度显著增加，直接证明增强的电导率与大幅增加的载流子群体相关。这些结果确立了结晶条件作为编程导电框架中电子态和电荷传输的主动参数。
英文摘要
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.
Comments10 pages, 4 figures
