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The development of portable electronic chemical sensors is key to solving a number of challenges, including monitoring environmental and industrial hazards, as well as understanding and improving human health. Framework materials possess several desirable characteristics that make them well-suited for electroanalytical applications, including high surface area, atomically precise distribution of active sites, and tunable properties that can be leveraged through modular reticular chemistry. This review highlights the emergence of conductive framework materials as active components in electrically transduced chemical sensors, including the development of new materials for the detection of a wide variety of analytes in both gas and liquid phase. The efforts to gain fundamental understanding of the molecular interactions and sensing mechanisms between framework materials and analytes are described, along with applications of these materials on portable and flexible substrates. The review suggests areas for further study, including the study of material−analyte interactions at the molecular level and the continued development of scalable methods for the integration of framework materials into low-power, portable sensing devices. 

This paper describes the use of the layered conductive metal−organic framework (MOF) (nickel)3-(hexahydroxytriphenylene) 2 [Ni3(HHTP)2] as a model system for understanding the process of self-assembly within this class of materials. We confirm and quantify experimentally the role of the oxidant in the synthetic process. Monitoring the deposition of Ni3(HHTP)2 with in situ infrared spectroscopy revealed that MOF formation is characterized by an initial induction period, followed by linear growth with respect to time. The presence and identity of oxidizing agents is critical for the coordination-driven self-assembly of these materials and impacts both the length of the induction period and the observed rate of MOF growth. A large excess of hydrogen peroxide results in a 2× increase in the observed deposition rate (9.6 ± 6.8 × 10−4 vs 5.0 ± 2.8 × 10−4 min−1) over standard reaction conditions, but leads to the formation of large, irregularly shaped particles. Slower deposition rates in the presence of oxygen favor the formation of uniformly sized nanorods (98 ± 38 × 25 ± 6 nm). These quantitative insights into the mechanism of HHTP-based MOF formation provide valuable information about the fundamental aspects of coordination and polymerization that are critical for nanoscale crystal engineering of structure−property relationships in this class of materials.