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.

Metal-organic frameworks (MOFs) represent a new class of hybrid organic-inorganic supramolecular materials comprised of ordered networks formed from organic electron donor linkers and metal cations. They can exhibit extremely high surface areas, as well as tunable pore size and functionality, and can act as hosts for a variety of guest molecules. Since their discovery, MOFs have enjoyed extensive exploration, with applications ranging from gas storage to drug delivery to sensing. This review covers advances in the MOF field from the past three years, focusing on applications, including gas separation, catalysis, drug delivery, optical and electronic applications, and sensing. We also summarize recent work on methods for MOF synthesis and computational modeling.

Metal‐Organic Frameworks: A Rapidly Growing Class of Versatile Nanoporous Materials

Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self-assembled through the coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre-designing or post-synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine.

Emerging Multifunctional Metal-Organic Framework Materials.

Metal–organic frameworks (MOFs) are intrinsically porous extended solids formed by coordination bonding between organic ligands and metal ions or clusters. High electrical conductivity is rare in M...

Electrically Conductive Metal-Organic Frameworks.

Role of solvents in coordination supramolecular systems

A highly stable pillared and double-walled zinc(II) metal-organic framework with regular nanochannels displays single-crystal to single-crystal transformation upon desolvation and a large quantity of iodine uptake, controlled release, and electrical conductivity elevation due to synergy between the iodine guests and the host framework.

Rigid Pillars and Double Walls in a Porous Metal-Organic Framework: Single-Crystal to Single-Crystal, Controlled Uptake and Release of Iodine and Electrical Conductivity

We present the syntheses, structural characterization, gas sorption, I2 uptake, and magnetic properties of a double-walled porous metal–organic framework, [CoII3(lac)2(pybz)2]·3DMF (1·3DMF, purple, where pybz = 4-pyridyl benzoate, lac = d- and l-lactate) and of its post-synthetic modified (PSM) congeners, [CoII3(lac)2(pybz)2]·xGuest (xGuest = 6MeOH, purple; 4.5EtOH, purple; 3PrOH, purple; 2C6H6, purple; 2.7I2, black), [CoII3(lac)2(pybz)2] (1, purple), [CoII3(pybz)2(lac)2(H2O)2]·7H2O (1a·7H2O, green), and [CoIIICoII2(pybz)2(lac)2(H2O)2]I·2H2O·1.5DMSO (1b·I–·2H2O·1.5DMSO, yellow, DMSO = dimethyl sulfoxide). Crystallography shows that the framework is not altered by the replacement of DMF by different solvents or by the removal of the solvent molecules during the single-crystal to single-crystal (SC-SC) transformations, while upon exchange with H2O or partial oxidation by molecular iodine, the crystallinity is affected. 1 absorbs N2, H2, CH4, CH3OH, C2H5OH, PrOH, C6H6, and I2, but once it is in contact with ...

Nanoporous Cobalt(II) MOF Exhibiting Four Magnetic Ground States and Changes in Gas Sorption upon Post-Synthetic Modification

The synthesis and characterization of a 4-fold-interpenetrated pseudodiamond metal–organic framework (MOF), CoII(pybz)2·2DMF [pybz = 4-(4-pyridyl)benzoate], are reported. N,N-Dimethylformamide (DMF) of the channels can be removed to give the porous framework, and it can also be exchanged for methanol, ethanol, benzene, and cyclohexane. It is a rare example of a stable MOF based on a single octahedral building unit. The single-crystal structures of CoII(pybz)2·2DMF, CoII(pybz)2, CoII(pybz)2·4MeOH, and CoII(pybz)2·2.5EtOH have been successfully determined. In all of them, the framework is marginally modified and contains a highly distorted and strained octahedral node of cobalt with two pyridine nitrogen atoms and two chelate carboxylate groups. In air, the crystals of CoII(pybz)2·2DMF readily change color from claret red to light pink. Thermogravimetric analysis and Raman spectroscopy indicate a change in coordination, where the carboxylate becomes monodentate and an additional two water molecules are coor...

A Porous 4-Fold-Interpenetrated Chiral Framework Exhibiting Vapochromism, Single-Crystal-to-Single-Crystal Solvent Exchange, Gas Sorption, and a Poisoning Effect

The invention discloses a microporous coordination polymer material, in particular to a microporous coordination polymer material with a three-dimensional double column-layer structure based on 4-(4-pyridyl) acidum benzoicum and lactic acid ligand and a preparation method and an application thereof. The chemical formula of M3(pybz)2(lac)2xSol refers to the microporous coordination polymer material, wherein, M is Fe, Co, Ni,Mn,Zn or Cd, pybz is 4-(4-pyridyl) acidum benzoicum radical, lac is lactate, and xSol is solvent molecule with adsorption quantity, wherein, x is the number of the absorbed solvent molecule. The invention has wide sources of raw materials for synthesizing the coordination polymer material, simple synthesizing steps, high rate of production, novel and particular structure and high thermal stability. The microporous coordination polymer material has nanometer pore canal and contains double holes and can be applied to fields of gas storage, molecule reaction flask, selective catalysis, etc.

Yan-Xi Tan

Papers

Rigid Pillars and Double Walls in a Porous Metal-Organic Framework: Single-Crystal to Single-Crystal, Controlled Uptake and Release of Iodine and Electrical Conductivity

Nanoporous Cobalt(II) MOF Exhibiting Four Magnetic Ground States and Changes in Gas Sorption upon Post-Synthetic Modification

A Porous 4-Fold-Interpenetrated Chiral Framework Exhibiting Vapochromism, Single-Crystal-to-Single-Crystal Solvent Exchange, Gas Sorption, and a Poisoning Effect

Microporous coordination polymer material based on 4-(4-pyridyl) acidum benzoicum and preparation method and application thereof