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Self-organization under out-of-equilibrium conditions is ubiquitous in natural systems for the generation of hierarchical solid-state patterns of complex structures with intricate properties. Efforts in applying this strategy to synthetic materials that mimic biological function have resulted in remarkable demonstrations of programmable self-healing and adaptive materials. However, the extension of these efforts to multifunctional stimuli-responsive solidstate materials across defined spatial distributions remains an unrealized technological opportunity. This paper describes the use of a nonequilibrium reaction−diffusion process to achieve the synthesis of a multifunctional stimuli-responsive electrically conductive metal−organic framework (cMOF) in a gelled medium with control over particle size and spatial periodicity on a macroscopic scale. Upon integration into chemiresistive devices, the resulting cMOF particles exhibit a size-dependent response toward hydrogen sulfide gas, as determined by their distinct surface-to-volume ratio, porosity, unique synthesis methodology, and unusual microcrystallite morphology compared to their counterparts obtained through bulk solution phase synthesis. Taken altogether, these achievements pave the way toward gaining access to functional nanomaterials with well-defined chemical composition, dimensions, and precisely tailored functions using far-from-equilibrium approaches. 

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. 

Abstract Bottom‐up self‐organization of unordered molecules into ordered, spatiotemporal patterns of complex structures through non‐equilibrium reaction–diffusion (RD) processes is ubiquitous in nature across all scales. Unlike many RD processes that typically lead to transient patterns, periodic precipitation reactions governed by the Liesegang phenomenon are distinguished by the formation of stable, permanent structures. This unique characteristic makes them valuable tools in the development of hierarchical multifunctional materials, an area that has seen significant progress in recent decades. This review summarizes the fundamental aspects of the Liesegang phenomenon, focusing on the key characteristics, compositional features, inherent properties, and formation mechanisms of Liesegang patterns in chemical systems, while also highlighting their occurrence in biological and geological settings. We discuss recent advancements in applying periodic precipitation to address global challenges in microelectronics and environmental monitoring, concluding with a forward‐looking perspective on the promising future applications of the Liesegang periodic precipitation in materials science, nanotechnology, medicine, and environmental engineering. 

This paper describes the scalable fabrication of smart electronic textiles (e-textiles) capable of simultaneous sensing, filtration, and detoxification of sulfur dioxide (SO2). The templated method converts pre-deposited copper metal into copper hydroxide, followed by conversion into a copper-based hexahydroxytriphenylene metal-organic framework (MOF) (Cu3(HHTP)2), to afford a large-area (10 × 10 cm2) conductive coating (sheet resistance = 0.1–0.3 MΩ). The resulting e-textiles achieve sensing (theoretical limit of detection [LOD] of 0.43 ppm), filtration (adsorption uptake of 1.9 and 0.83 mmol g−1 for MOF powder and MOF/textile, respectively, at 1 bar and 298 K), and detoxification (redox conversion of SO2 gas into solid sulfate) due to the selective material-analyte interactions. This scalable method for generating e-textiles is a promising approach for the fabrication of smart membrane materials with multifunctional performance characteristics.