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) have received much attention because of their attractive properties. They show great potential applications in many fields. An emerging trend in MOF research is hybridization with flexible materials, which is the subject of this review. Polymers possess a variety of unique attributes, such as softness, thermal and chemical stability, and optoelectrical properties that can be integrated with MOFs to make hybrids with sophisticated architectures. Hybridization of MOFs and polymers is producing new and versatile materials that exhibit peculiar properties hard to realize with the individual components. This review article focuses on the methodology for hybridization of MOFs and polymers, as well as the intriguing functions of hybrid materials.

Hybridization of MOFs and polymers

Li-ion battery commercialized by Sony in 1991 has the highest energy-density among practical rechargeable batteries and is widely used in electronic devices, electric vehicles, and stationary energy storage system in the world. Moreover, the battery market is rapidly growing in the world and further fast-growing is expected. With expansion of the demand and applications, price of lithium and cobalt resources is increasing. We are, therefore, motivated to study Na- and K-ion batteries for stationary energy storage system because of much abundant Na and K resources and the wide distribution in the world. In this account, we review developments of Na- and K-ion batteries with mainly introducing our previous and present researches in comparison to that of Li-ion battery.

Towards K-Ion and Na-Ion Batteries as "Beyond Li-Ion".

Metal-organic frameworks (MOFs) as chemical sensors have developed rapidly in recent years. There have been many papers concerning this field and interest is still growing. The reason is that the specific merits of MOFs can be utilized to enhance sensitivity and selectivity by various energy/charge transfers occurring among different ligands, ligand, and metal centers, such as from ligands to metal centers or metal centers to ligands, as well as from MOF skeletons to guest species. This review intends to provide an update on recent progress in various applications of different MOF-based sensors on the basis of their luminescent and electrochemical responses towards small molecules, gas molecules, ions (cations and anions), pH, humidity, temperature, and biomolecules. MOF-based sensors function by utilizing different mechanisms, including luminescent responses of "turn-on" and "turn-off", as well as electrochemical responses.

Chemical Sensors Based on Metal–Organic Frameworks

Metal–organic frameworks (MOFs) have emerged as particularly exciting inorganic–organic hybrid porous materials which can be simply self-assembled from their corresponding inorganic metal ions/clusters with organic linkers. MOFs can combine the inherent physical and chemical properties of both inorganic and organic photonic units due to their inorganic–organic hybrid nature. Furthermore, the pores within MOFs can also be utilized to encapsulate a large number of guest species as photonic units. The vast combination possibilities, synergistic effects, as well as controllable and ordered arrangements of multiple photonic units (MPUs) have distinguished MOFs from other inorganic and organic photonic materials and enabled them to be a promising platform to realize novel photonic functional applications. In this review, we summarize the recent and important progress in the design and construction of photonic MOFs, as well as their various applications in luminescence sensing, white-light emission, photocatalysis, nonlinear optics, lasing devices, data storage, and biomedicine. In addition, we highlight the construction strategy and the synergistic effects of MOFs towards achieving high performance and novel photonic functions. Finally, we also outline the challenges in these fields and put forward the prospects and directions for future development.

Photonic functional metal-organic frameworks.

Multiphoton upconversion is a process where two or more photons are absorbed simultaneously to excite an electron to an excited state and, subsequently, the relaxation of electron gives rise to the emission of a photon with frequency greater than those of the absorbed photons. Materials possessing such property attracted attention due to applications in biological imaging, photodynamic therapy, three-dimensional optical data storage, frequency-upconverted lasing and optical power limiting. Here we report four-photon upconversion in metal-organic frameworks containing the ligand, trans, trans-9,10-bis(4-pyridylethenyl)anthracene. The ligand has a symmetrical acceptor-π-donor-π-acceptor structure and a singlet biradical electronic ground state, which boosted its multiphoton absorption cross-sections. We demonstrate that the upconversion efficiency can be enhanced by Forster resonance energy transfer within host-guest metal-organic frameworks consisting of encapsulated high quantum yielding guest molecules. Using these strategies, metal-organic framework materials, which can exhibit frequency-upconverted photoluminescence excited by simultaneous multiphoton absorption, can be rationally designed and synthesized.

/pdf/multiphoton-harvesting-metal-organic-frameworks-3k8zh1jteu.pdf

Multiphoton harvesting metal-organic frameworks.

Getting suitable crystals for single-crystal X-ray crystallographic analysis still remains an art. Obtaining single crystals of metal-organic frameworks (MOFs) containing organic polymers poses even greater challenges. Here we demonstrate the formation of a syndiotactic organic polymer ligand inside a MOF by quantitative [2+2] photopolymerization reaction in a single-crystal-to-single-crystal manner. The spacer ligands with trans,trans,trans-conformation in the pillared-layer MOF with guest water molecules in the channels, undergo pedal motion to trans,cis,trans-conformation prior to [2+2] photo-cycloaddition reaction and yield single crystals of MOF containing two-dimensional coordination polymers fused with the organic polymer ligands. We also show that the organic polymer in the single crystals can be depolymerized reversibly by cleaving the cyclobutane rings upon heating. These MOFs also show interesting photoluminescent properties and sensing of small organic molecules.

Formation of a Syndiotactic Organic Polymer Inside a MOF by a [2+2] Photo-Polymerization Reaction.

As a recently emerged class of inorganic–organic hybrid crystals, metal–organic frameworks (MOFs) have been investigated for their capabilities for doubling light frequency. We report, for the first time, our observation of an efficient coherent up-conversion via third harmonic generation (THG) in a MOF. It is achieved by utilizing a MOF with a constituent ligand that possesses significant third-order nonlinear optical (NLO) responses. Our THG measurements at fundamental wavelengths ranging from 1200 to 1600 nm show that the MOF constructed with the An2Py ligand exhibits an effective χ(3) value that is 3 orders of magnitude greater than α-quartz. Our findings demonstrate a new avenue to realize efficient third-order NLO responses by utilizing MOFs consisting of strong third-order NLO ligands.

Efficient Third Harmonic Generation in a Metal–Organic Framework

This perspective focusses on the solid-state reactivity and structural transformation driven by photochemical methods in discrete metal complexes, organometallic compounds, metallo-macrocycles and cages. Changes in the metal-metal bond distances, racemization of chiral centres, fusion of cages, formation of coordination polymers, expected [2 + 2] and [4 + 4] cycloaddition products, unusual phenyl-olefin dimerization, and linkage isomerization of -SO2, -NO & -NO2 ligands cause the structural transformations. Of these, [2 + 2] photo-cycloaddition reactions have been widely studied and the photoreactions are made possible by various supramolecular interactions including hydrogen bonds, metallophilic, ππ and C-Hπ interactions, ligand design and metallic clips to bring the reactive functional groups closely into correct orientation close to the transition state. These photoreactions are often accompanied by crystal bending, mechanical motion, and changes in the magnetic and photoluminescence properties. In several cases, the single crystals have been preserved at the end of the reactions, which are known as single-crystal-to-single-crystal (SCSC) reactions.

Hong Sheng Quah

Papers

Multiphoton harvesting metal-organic frameworks.

Formation of a Syndiotactic Organic Polymer Inside a MOF by a [2+2] Photo-Polymerization Reaction.

Efficient Third Harmonic Generation in a Metal–Organic Framework

Photochemical reactions of metal complexes in the solid state.

Engineering solid state structural transformations of metal complexes