As functional electrical devices advance, new strategies for regulating electrical properties are essential for achieving diverse electrical performance. In this study, molecular heterojunction rectifiers are constructed by connecting porphyrinic 2D metal–organic framework (2D MOF) nanosheets and oligophenylene thiols self‐assembled monolayers (OPT SAMs) within metal electrodes. The rectification characteristics can be tuned by the molecular length of OPT and the coordinated metal atom in the center of 2D MOFs. Specifically, a rectification ratio of more than 1.67 orders of magnitude is achieved in the heterojunction composed of 2D Zn‐TCPP MOF nanosheet (TCCP, tetrakis(4‐carboxyphenyl) porphyrin) and OPT3 SAM. Combining Kelvin probe force microscopy measurements and first‐principles calculations of the 2D MOF nanosheets, it elucidates that the rectification variations come from the adjustment of energy level alignment at OPT SAMs//2D MOF interface, leading to asymmetric charge transport with the voltage polarities. This strategy can be further extended to Cu‐MOF nanosheets, which also exhibit rectification behaviors when placed on OPT2 SAMs. This work provides a universal and flexible strategy for regulating the electrical behaviors of MOFs without the need for specific design and synthesis, paving the way for the development of MOF‐based functional electronic devices.

中文翻译：

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2D 卟啉金属-有机框架纳米片分子异质结中的可调谐整流


随着功能性电气器件的进步，调节电气特性的新策略对于实现不同的电气性能至关重要。在本研究中，通过在金属电极内连接卟啉 2D 金属有机框架 （2D MOF） 纳米片和寡苯硫醇自组装单层 （OPT SAM） 来构建分子异质结整流器。整流特性可以通过 OPT 的分子长度和 2D MOF 中心的配位金属原子来调节。具体来说，在由 2D Zn-TCPP MOF 纳米片 （TCCP，四（4-羧基苯基） 卟啉） 和 OPT3 SAM 组成的异质结中实现了超过 1.67 个数量级的整流比。结合开尔文探针力显微镜测量和 2D MOF 纳米片的第一性原理计算，它阐明了整流变化来自 OPT SAMs//2D MOF 界面处能量能级对准的调整，导致电压极性的不对称电荷传输。这种策略可以进一步扩展到 Cu-MOF 纳米片，当放置在 OPT2 SAM 上时，它也表现出整流行为。这项工作提供了一种通用且灵活的策略来调节 MOF 的电行为，而无需特定的设计和合成，为基于 MOF 的功能性电子器件的开发铺平了道路。