Metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) are open, crystalline supramolecular coordination architectures with porous facets. These chemically tailorable framework materials are the subject of intense and expansive research, and are particularly relevant in the fields of sensory materials and device engineering. As the subfield of MOF-based sensing has developed, many diverse chemical functionalities have been carefully and rationally implanted into the coordination nanospace of MOF materials. MOFs with widely varied fluorometric sensing properties have been developed using the design principles of crystal engineering and structure–property correlations, resulting in a large and rapidly growing body of literature. This work has led to advancements in a number of crucial sensing domains, including biomolecules, environmental toxins, explosives, ionic species, and many others. Furthermore, new classes of MOF sensory materials utilizing advanced signal transduction by devices based on MOF photonic crystals and thin films have been developed. This comprehensive review summarizes the topical developments in the field of luminescent MOF and MOF-based photonic crystals/thin film sensory materials.

Metal-organic frameworks: functional luminescent and photonic materials for sensing applications.

https://persianmof.weebly.com/uploads/4/8/8/3/48832931/chem._rev._2014,_114,_10575.pdf

Water stability and adsorption in metal-organic frameworks.

Advances in flexible and functional metal–organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009–2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host–guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal–organic frameworks for separation, catalysis, sensing, and biomedicine.

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Flexible metal–organic frameworks

Owing to their outstanding structural, chemical, and functional diversity, metal-organic frameworks (MOFs) have attracted considerable attention over the last two decades in a variety of energy-related applications. Notably missing among these, until recently, were applications that required good charge transport coexisting with porosity and high surface area. Although most MOFs are electrical insulators, several materials in this class have recently demonstrated excellent electrical conductivity and high charge mobility. Herein we review the synthetic and electronic design strategies that have been employed thus far for producing frameworks with permanent porosity and long-range charge transport properties. In addition, key experiments that have been employed to demonstrate electrical transport, as well as selected applications for this subclass of MOFs, will be discussed.

Electrically Conductive Porous Metal–Organic Frameworks

Triazoles and tetrazoles: Prime ligands to generate remarkable coordination materials

Mohamad Hmadeh,†,‡ Zheng Lu,†,‡ Zheng Liu, Felipe Gandara,†,‡ Hiroyasu Furukawa,†,‡ Shun Wan,†,‡ Veronica Augustyn, Rui Chang, Lei Liao,‡ Fei Zhou, Emilie Perre, Vidvuds Ozolins, Kazu Suenaga, Xiangfeng Duan,‡ Bruce Dunn, Yasuaki Yamamto, Osamu Terasaki, and Omar M. Yaghi*,†,‡,#,¶ †Center for Reticular Chemistry, Center for Global Mentoring, ‡Department of Chemistry and Biochemistry, and Department of Materials Science and Engineering, University of California, Los Angeles, California 90095, United States Nanotube Research Center, AIST, Tsukuba 305-8565, Japan SMBU, JEOL Ltd., Akishima, Tokyo 196-8558, Japan Department of Materials and Environmental Chemistry and EXSELENT, Stockholm University, Stockholm, Sweden Graduate School of EEWS (WCU), Korea

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New Porous Crystals of Extended Metal-Catecholates

Approaches for synthesizing breathing MOFs by exploiting dimensional rigidity

Two imidazolate-metal based rhombic dodecahedra (termed MOP-100 and MOP-101) were designed and prepared from [(NH(3))(4)Pd(NO(3))(2)] and hydrogen tetrakis(1-imidazolyl)borate or hydrogen tetrakis(4-methyl-1-imidazolyl)borate in a concentrated ammonium hydroxide solution at 85 degrees C. Both rhombic dodecahedra show unusual chemical stability in acidic and basic solutions as well as common organic solvents. Permanent porosity was examined by gas adsorption studies. From the N(2) isotherm for MOP-101, the Langmuir and BET surface areas of MOP-101 were calculated to be 350 and 280 m(2) g(-1), respectively. Anion exchange experiments confirmed the internal cavities of such polyhedra are accessible.

http://yaghi.berkeley.edu/pdfPublications/09synthStructure.pdf

Synthesis and structure of chemically stable metal-organic polyhedra.

A dimeric macrocyclic tetra-N-heterocyclic carbene (NHC) silver complex was synthesized and shown to successfully extend transmetallation of polydentate NHCs beyond bidentate NHCs. The silver complex was utilized in the preparation of a variety of monomeric tetra-NHC complexes ranging from early first row to late third row transition metals in moderate to high yield for a total of nine examples of transmetallation. Among these complexes are rare examples of silver transmetallation with first row transition metals: chromium, iron, and cobalt. Additionally, the first examples of tetracarbenes on chromium and gold are reported. All compounds were characterized by single crystal X-ray diffraction, ESI-MS, and spectroscopic techniques.

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Zheng Lu

Papers

New Porous Crystals of Extended Metal-Catecholates

Approaches for synthesizing breathing MOFs by exploiting dimensional rigidity

Synthesis and structure of chemically stable metal-organic polyhedra.

Exploiting a dimeric silver transmetallating reagent to synthesize macrocyclic tetracarbene complexes

Synthesis and structure of a boron cation supported by a β-diketiminate ligand