Because of their outstanding structural, chemical, and functional diversity, metal‐organic frameworks (MOFs) have brought about worldwide interest over the last 2 decades, which have been utilized in a wide range of applications in the fields of gas separation, storage, catalysis, and drug delivery. However, among these applications, MOFs are almost used in the form of powder. Due to their fragility and difficulty in preparing large‐area thin film materials, the study of MOF films and their electronic properties is a challenging problem in the research of MOFs. Owing to the low‐energy charge transport mode, most MOF films are essentially insulating, which largely limits their applications in fields where electronic charge transport takes place, such as electronics or electrochemistry. So, the introduction of conductivity into the MOF films opens new avenues for their applications in electrochemical sensing, supercapacitors, batteries, electrocatalysis, and electronic devices and makes the research on and with MOF films very active. Herein, the latest progress of conductive MOF films, including the preparation of MOF films, the design and adjustment strategies for constructing intrinsic and doping conductive MOF films, and their applications are reviewed. In addition, the numerous challenges of conductive MOF films are also elaborated.

Doping is an important strategy for effectively regulating the charge carrier concentration of semiconducting materials. In this study, the electronic properties of organic-inorganic hybrid semiconducting polymers, synthesized via in situ controlled vapor phase infiltration (VPI) of poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-C14) with the metal precursors molybdenum pentachloride (MoCl5) and titanium tetrachloride (TiCl4), were altered and characterized. The conductivities of the infiltration-doped PBTTT-C14 thin films were enhanced by up to 9 and 4 orders of magnitude, respectively. The significantly improved electrical properties may result from interactions between metal atoms in the metal precursors and sulfur of the thiophene rings, thus forming new chemical bonds. Importantly, VPI doping has little influence on the structure of the PBTTT-C14 thin films. Even if various dopant molecules infiltrate the polymer matrix, the interlayer spacing of the films will inevitably expand, but it has negligible effects on the overall morphology and structure of the film. Also, Lewis acid-doped PBTTT-C14 thin films exhibited excellent environmental stability. Therefore, the VPI-based doping process has great potential for use in processing high-quality conductive polymer films.

Recently, the flexibility of 2D conductive metal–organic frameworks (MOFs) is an important precondition for manufacturing high‐performance smart electronic devices. Preparation of MOFs thin film has drawn much attention, and increasingly more MOF thin films have been deposited on different rigid substrates like glass, silicon, and metal electrodes. However, they do not meet the requirements for flexible materials, such as wearable electronic devices. Here, the fabric‐based composites (the integration of MOFs and fabric materials) can solve this problem. Insulating polyester fabric is chosen as a flexible substrate and atom layer deposition (ALD) and the layer‐by‐layer (LBL) method (also called the liquid phase epitaxy method) are combined to synthesize Cu3(BTC)2 thin film. 7,7,8,8‐tetracyanoquinodimethane (TCNQ) and polypyrrole (PPy) are chosen to improve the conductivity of the MOF thin films. The conductivity of Cu3(BTC)2 thin film is improved by more than four orders of magnitude compared to that of the original sample. This research shows that the large‐area lightweight fabric‐based Cu3(BTC)2 thin films, which possess excellent uniformity and flexibility and controllable thickness, can be prepared at room temperature; this allows MOFs to be applied in more areas, such as large‐area electronic devices and smart wearable sensing equipment.

Integration of metal–organic frameworks (MOFs) and flexible fabrics has been recently considered as a promising strategy applied in wearable electronic devices. We synthesized a flexible fabric-based Cu-HHTP film consisted of Cu2+ ions and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) via a self-sacrificial template method. The obtained Cu-HHTP film displays an outstanding nanostructured surface and uniformity. Iodine molecules are first introduced into the pores of Cu-HHTP to investigate the influence of guest molecules on electrical conductivity in a 2D guest–host system. After doping, the conductivity of the Cu-HHTP film shows an increased dependent on the doping time, and the maximum value is more than 30 times that of the original MOFs. The enhanced electrical conductivity results from an intriguing redox interaction occurred between the confined iodine molecules and the framework. The organic ligands are oxidized by iodine molecules, and generating new ions allows for subsequent participation in the regulation of the mixed valence bands of copper ions in MOFs, changing the ratio of Cu2+/Cu+, promoting the charge transport of the framework, and then synergistically enhancing the electronic conductivity. This study successfully prepared a flexible fabric-based conductive I2@Cu-HHTP film and presented insights into revealing the behavior of iodine molecules after entering the Cu-HHTP pores, expanding the possibilities of Cu-HHTP used in flexible wearable electronics.